1. Ciencia

Bilbao, 4-7 Noviembre 2014
Bilbao, 4-7 Noviembre 2014
Bilbao, 4-7 Noviembre 2014
Martes 4
9:00
9:30
9:45
Miércoles 5
Jueves 6
PSA-2: A. de la Escosura
PSC-1: J. J. Cid
CO-10: A. Correa
CO-26: M. Artola
CO-11: I. León
CO-27: M. Ortuño
CO-12: M. Montesinos
CO-28: C. Glez Rguez
CO-38: P. Montaño
10:15
CO-29: V. Ovejas
Sigma Aldrich
10:30
CO-39: M. Frías
CO-30: M. Trigo
CO-40: A. Macario
10:45
Pausa Café
Sesión de Posters 1
Pausa Café
Sesión de Posters 2
HT-2: J. M. Muñoz
HT-4: A. Mateo
Charla JIQ
11:45
CO-13: A. Mtnez Cuezva
CO-31: D. Glez Rguez
CO-42: S. Sierra
12:00
CO-14: J. García Álvarez
CO-32: M. Vallejo
CO-43: C. Casadevall
Registro
Hotel Jardines
de Albia
CO-15: I. Riaño
CO-33: A. Díaz Moscoso
CO-44: J. V. Alegre
CO-16: C. Calabrese
CO-34: S. Luaces
CO-45: C. Rodrigo
12:45
13:00
14:00
14:45
15:15
12:45
Registro Bizkaia Aretoa
Acto de
Inauguración
Pausa Comida
PSA-1: M. Tortosa
Entrega de Premios
CO-01: G. Zango
CO-18: A. Fdez Barquín
16:15
CO-02: E. J. Juárez
CO-19: A. Parra
16:30
CO-03: C. Are
CO-20: R. Donamaría
16:45
CO-04: A. Vellé
CO-21: B. Vaz
17:00
CO-05: S. Álvarez
Pausa Café
HT-1: R. Ponce
HT-3: C. Martí
18:05
CO-06: M. G. Retamosa
CO-22: P. Saura
18:20
CO-07: F. Gonell
CO-23: J. Etxabe
18:35
CO-08: S. Morales
CO-24: A. Mtnez Mtnez
18:50
CO-09: A. Rguez
CO-25: R. M. Fratila
21:00
10:05
10:20
10:35
10:50
11:05
11:35
11:50
12:05
12:20
12:35
12:50
CO-35: Z. Monasterio
CO-36: S. Mitchell
PSA = Premio Sigma Aldrich
PSC = Premio SusChem
Taller de Empresas
HT = Comunicación Hot-topic
CO = Comunicación Oral
Sesión de Posters 1=P-01-P42
Sesión de Posters 2=P-43-P86
Pausa Café
Sesión de Posters 1
17:45
19:05
Acto de Clausura
9:50
PSC-2: S. Gonell
CO-17: S. Vela
16:00
17:15
Pausa Comida
9:30
13:15
PSA-3: R. Vicente
15:30
15:45
CO-41: R. Losantos
Pausa Café
11:25
12:30
HT-5: A. Fdez Tejada
CO-37: C. García García
10:00
12:15
Viernes 7
Pausa Café
Sesión de Posters 2
Taller de Empresas
VISITA GUIADA
CENA DE GALA
π
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Bilbao, 4-7 Noviembre 2014
Bilbao, 4-7 Noviembre 2014
Bilbao, 4-7 Noviembre 2014
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Bilbao, 4-7 Noviembre 2014
Ana Caballero Bevia se licenció en la Universidad de Sevilla en 1999 e inició su doctorado en
la Universidad de Huelva ese mismo año con los profesores Tomás R. Belderrain y Pedro J.
Pérez. Se doctoró en el año 2004, con Premio Extraordinario de Doctorado de la Universidad
de Huelva. Posteriormente, de 2005 a 2007, se trasladó al Laboratoire de Chimie de
Coordination (LCC) del CNRS de Toulouse (Francia) para realizar una estancia posdoctoral
en el grupo de la profesora Sylviane Sabo-Etienne gracias a una beca del Ministerio de
Educación. En 2007 obtuvo un contrato Ramón y Cajal, reincorporándose a la Universidad de
Huelva. Actualmente ocupa un puesto de profesora contratada doctora en esta Universidad.
Sus líneas principales de investigación se basan en la funcionalización catalítica de enlaces CH poco activados de distintos hidrocarburos, principalmente de metano.
Publicaciones destacadas:
M. A. Fuentes, A. Olmos, B. K. Muñoz, K. Jacob, M. E. González-Núñez, R. Mello, G.
Asensio, A. Caballero,* M. Etienne y P. J. Pérez, Chem. Eur. J. 2014.
10.1002/chem.201403217
M. A. Fuentes, B. K. Muñoz, K. Jacob, L. Vendier, A. Caballero,* M. Etienne y P. J. Pérez.
"Functionalization of Non-activated C-H Bonds of Alkanes: An Effective and Recyclable
Catalytic System Based on Fluorinated Silver Catalysts and Solvents". Chem. Eur.
J. 2013, 19, 1327-1334.
A. Caballero, E. Despagnet-Ayoub, M. M. Díaz-Requejo, A. Díaz-Rodríguez, M. E.
González-Núñez, R. Mello, B. K. Muñoz, W. Solo Ojo, G. Asensio, M. Etienne y P. J. Pérez.
"Silver-Catalyzed C-C Bond Formation Between Methane and Ethyl Diazoacetate in
Supercritical CO2". Science 2011, 332, 835–838.
A. Caballero, M. M. Díaz-Requejo, T. R. Belderrain, M. C. Nicasio, S. Trofimenko y P. J.
Pérez. "Highly Regioselective Functionalization of Aliphatic Carbon-Hydrogen Bonds with a
Perbromohomoscorpionate Copper(I) Catalyst". J. Am. Chem. Soc. 2003, 125, 1446-1447.
Bilbao, 4-7 Noviembre 2014
Mariola Tortosa se licenció en Ciencias Químicas por la Universidad Autónoma de Madrid,
recibiendo el premio extraordinario de licenciatura. Ese mismo año inició su tesis doctoral en
el Instituto de Química Orgánica del CSIC bajo la dirección del Dr. Roberto Fernández de la
Pradilla. En 2004 recibió el premio Lilly para estudiantes de doctorado y en 2005 se trasladó a
The Scripps Research Institute (Florida, EEUU) para trabajar en el grupo del profesor
William Roush. Durante este periodo trabajó en la síntesis total de Superstolide A. En 2008
volvió al Instituto de Química Orgánica General (CSIC, Madrid,) con un contrato Juan de la
Cierva. Desde 2011 forma parte del departamento de Química Orgánica de la Universidad
Autónoma de Madrid como contratado Ramón y Cajal. En 2013, recibió una Starting-Grant
del European Research Council para desarrollar el proyecto "Design and applications of
Unconventional Borylation Reactions". Su línea actual de investigación se centra en el
desarrollo de nuevas reacciones de borilación y su aplicación a la síntesis de productos
biológicamente activos. Mariola es co-autora de 27 trabajos y dos capítulos de libro,
publicados en revistas científicas de alto impacto. En 2014, ha recibido el premio Eli Lilly
para Jóvenes Investigadores.
Publicaciones destacadas:
1. R. Alfaro, A. Parra, J. Alemán, J. L. Garcia Ruano, M. Tortosa.* "Copper(I)-Catalyzed
Formal Carboboration of Alkynes: Synthesis of Tri- and Tetrasubstituted
Vinylboronates". J. Am. Chem. Soc. 2012, 134, 15165-15168.
2. M. Tortosa.* "Synthesis of Syn and Anti 1,4-Diols by Copper Catalyzed Boration of
Allylic Epoxides". Angew. Chem. Int. Ed. 2011, 50, 3950-3953.
3. M. Tortosa, N. A. Yakelis, W. R. Roush. "Total Synthesis of (+)-Superstolide A". J. Am.
Chem. Soc. 2008, 130, 2722-2723.
Nucleophilic Boron: New Opportunities for Carbon-Boron Bond Formation
Mariola Tortosa
Departamento de Química Orgánica, Universidad Autónoma de Madrid, 28049 Madrid
[email protected]
Boronic esters are versatile synthetic intermediates for the preparation of a wide range of
organic molecules. The development of new methods to create C-B bonds in an efficient,
inexpensive, and environmentally friendly way is therefore an important challenge in organic
chemistry. Traditionally, the methods to form C-B bonds have mostly been based on the
electrophilic nature of boron. While this classical approach works well for reactions with
nucleophilic partners, it naturally limits the types of boron compounds that can be prepared.
Recently, copper-catalyzed borylations have emerged as a new source of nucleophilic boron.
The lower price and toxicity of copper versus other transition metals and the unique reactivity
of the boryl-copper intermediates make these processes particularly attractive.1 Inspired by
unsolved problems found in the total synthesis of complex molecules, we have used borylcopper species to synthesize 1,4-diols,2 trisubstituted alkenes,3 and cyclopropyl derivatives.
These and other preliminary studies ongoing in our group will be presented in this talk.
Figure 1
Acknowledgements: financial support from Spanish Government (CTQ-2012-35957) and the
European Research Council (ERC Starting Grant DAUBOR) is gratefully acknowledged.
________________________________________________
1 For selected references, see: a) H. Ito, C. Kawakami, M. Sawamura, J. Am. Chem. Soc. 2005, 127, 16034. b)
J-E. Lee, J. Yun, Angew. Chem. Int. Ed. 2008, 47, 145. c) Jang, H.; Zhugralin, A. R.; Lee, Y.; Hoveyda, A.
M. J. Am. Chem. Soc. 2011, 133, 7859.
2 Tortosa M. Angew. Chem. Int. Ed. 2011, 50, 3950.
3 Alfaro, R.; Parra, A.; Alemán, J.; García Ruano, J. L.; Tortosa, M. J. Am. Chem. Soc. 2012, 134, 15165.
Bilbao, 4-7 Noviembre 2014
Andrés de la Escosura se licenció en Ciencias Químicas por la Universidad Autónoma de
Madrid en el año 2000. Realizó su tesis en el grupo del Prof. Tomás Torres, trabajando en la
síntesis y el estudio de sistemas moleculares, supramoleculares y poliméricos basados en
ftalocianinas. Se doctoró en el año 2005, siendo Profesor Ayudante desde Octubre de 2003.
Realizó también una estancia de 3 meses en el California Institute of Technology (Caltech)
bajo la supervisión del Prof. Robert Grubbs. Posteriormente, llevó a cabo estudios
postdoctorales (2006-2008) en la Radboud University Nijmegen (Holanda), en el grupo del
Prof. Roeland Nolte, donde disfrutó de la prestigiosa beca Marie Curie Intraeuropea y trabajó
en el uso de cápsides virales como nanoreactores. Tras su reincorporación a la UAM en 2009,
primero como Profesor Ayudante Doctor y desde febrero de 2012 como Investigador Ramón
y Cajal, ha estado a cargo de distintos proyectos, siempre en la interfase entre la química y la
biología. Su investigación se centra en la construcción de nanomateriales híbridos para
aplicaciones biomédicas, aunque también está empezando a explorar diversos aspectos dentro
del campo de la química de sistemas y el origen de la vida.
Publicaciones destacadas:
1. D. Luque, A. de la Escosura,* J. Snijder, M. Brasch, R. J. Burnley, M. S. T. Koay, J. L.
Carrascosa, G. J. L. Wuite, W. H. Roos, A. J. R. Heck, J. J. L. M. Cornelissen, T. Torres y
J. R. Castón. "Self-Assembly and Characterization of Small and Monodisperse Dye
Nanospheres in a Protein Cage". Chem. Sci. 2014, 5, 575-581.
2. K. Ruiz Mirazo, C. Briones y A. de la Escosura.* "Prebiotic Systems Chemistry: New
Perspectives for the Origins of Life". Chem. Rev. 2014, 114, 285-366.
3. M. Brasch, A. de la Escosura,* Y. Ma, C. Uetrecht, A. J. R. Heck, T. Torres y J. J. L. M.
Cornelissen. "Encapsulation of Phthalocyanine Supramolecular Stacks into Virus-Like
Particles". J. Am. Chem. Soc. 2011, 133, 6878-6881.
4. de la Escosura,* P. G. A. Janssen, A. P. H. J. Schenning, R. J. M. Nolte y J. J. L. M.
Cornelissen. "Encapsulation of DNA-Templated Chromophore Assemblies within Virus
Protein Nanotubes". Angew. Chem. Int. Ed. 2010, 49, 5335-5338.
Exploring Different Nanoplatforms for Enhancement of Photosensitizers
Andrés de la Escosura, Eduardo Anaya-Plaza, Francesca Setaro, Eveline van de Winckel, Ana
I. Aljarilla, Joona Mikkila, Tomás Torres and José R. Castón
Organic Chemistry Department, Universidad Autónoma de Madrid, 28049 Cantoblanco
[email protected]
In this presentation, we will discuss novel methodologies to prepare photosensitizing
compounds with adequate solubility features and functional groups for their attachment to
different nanostructures (Figure 1). The goal is to describe a set of powerful and versatile
strategies for the loading of phthalocyanines (Pc) and other organic dyes in protein cages,1
and in organic and inorganic nanoparticles traditionally used as drug carriers. With these
strategies, the transport of the photosensitizer towards diseased tissues, for example in
photodynamic therapy (PDT) treatments, can be facilitated by the mentioned biocompatible
nanostructures.2,3 Our studies also pursue the decoration of single-wall carbon nanotubes
(SWCNT) with Pc derivatives specifically designed to interact with them through
supramolecular interactions. This second line of research will open the way to green organic
solar cells, that is, photovoltaic devices processed from aqueous solutions.4
Figure 1: different nanoplatforms that can be used as carriers of photosensitizers (PS)
This work was supported by the Spanish Ministry MEC and MICINN (CTQ-201124187/BQU), Consolider-Ingenio Nanociencia Molecular (CSD2007-00010), CAM
(MADRISOLAR-2, S2009/PPQ/1533) and UE (FP7-NMP-2012-LARGE-6, Nº: 310337-2).
1 de la Escosura, A.; Janssen, P.; Schenning, A.; Nolte, R. J. M.; Cornelissen, J. J. L. M. Angew. Chem. Int. Ed.
2010, 49, 5335.
2 Brasch, M.; de la Escosura, A.; Ma, Y.; Uetrecht, C.; Heck, A. J. R.; Torres, T.; Cornelissen, J. J. L. M. J.
Am. Chem. Soc. 2011, 133, 6878.
3 Luque, D.; de la Escosura, A.; Snijder, J.; Brasch, M.; Burnley, R. J.; Koay, M. S. T.; Carrascosa, J. L.; Roos,
W. H.; Heck, A. J. R.; Cornelissen, J. J. L. M.; Torres, T.; Castón, J. R. Chem. Sci. 2014, 5, 575.
4 Ryan, J. W.; Anaya-Plaza, E.; de la Escosura, A.; Torres, T.; Palomares, E. Chem. Commun. 2012, 48, 6094.
Bilbao, 4-7 Noviembre 2014
Rubén Vicente (Guadalajara, 1977) se licenció en Química en 2000 en la Universidad
Complutense de Madrid (UCM), donde trabajó durante un año con el Prof. Miguel A. Sierra
(UCM) en síntesis de beta-lactamas. Después de un año alejado de la química, en 2002 se
trasladó a la Universidad de Oviedo. Obtuvo su doctorado (cum laude) bajo la dirección del
Prof. José Barluenga en 2006 trabajando en aplicaciones sintéticas de complejos carbeno de
Fischer. Durante este periodo realizó dos estancias en la Universidad de Bonn (Prof. Kilian
Muñiz) y el Boston College (Prof. Marc L. Snapper). Realizó una estancia posdoctoral de tres
años (2007-2009, Becario posdoctoral MEC y Alexander von Humboldt Foundation) en el
grupo del Prof. Lutz Ackermann (Georg-August-University Goettingen), donde su
investigación se centró en el estudio de reacciones de funcionalización de enlaces C–H. En
2010 volvió a la Universidad de Oviedo como investigador contratado "Juan de la Cierva" y
desde 2012 es investigador "Ramón y Cajal". Entre sus intereses en química se incluyen el
descubrimiento de nuevos modos de reactividad y el desarrollo de procesos catalíticos
sostenibles.
Publicaciones destacadas:
1. M. J. González, E. López y R. Vicente.* "Rhodium-catalyzed carbene transfer to alkynes
via 2-furylcarbenes generated from enynones". Chem. Commun. 2014, 50, 5379-5381.
2. J. González, J. González, C. Pérez-Calleja, L. A. López y R. Vicente.* "Zinc-Catalyzed
Synthesis of Functionalized Furans and Triarylmethanes from Enynones and Alcohols or
Azoles: Dual X-H Bond Activation by Zinc". Angew. Chem. Int. Ed. 2013, 52, 5853-5857.
3. V. Pirovano, L. Decataldo, E. Rossi y R. Vicente.* "Gold-catalyzed synthesis of
tetrahydrocarbazole derivatives through an intermolecular cycloaddition of vinyl indoles
and N-allenamides". Chem. Commun.2013, 49, 3594-3596.
4. R.Vicente, J. González, L. Riesgo, J. González y L. A. López. "Catalytic Generation of
Zinc Carbenes from Alkynes: Zinc-Catalyzed Cyclopropanation and Si-H Bond Insertion
Reactions". Angew. Chem. Int. Ed.2012, 51, 8063-8067.
Metal-Catalyzed Alkyne Activation: a Trip from Gold to Zinc Catalysis
Rubén Vicente
Departamento de Química Orgánica e Inorgánica & Instituto de Química Organometálica “Enrique Moles”,
Universidad de Oviedo, c/ Julián Clavería 8, 33006-Oviedo
[email protected]
Electrophilic activation of alkynes by means of transition metal catalysis has become a
valuable tool for organic synthesis. These transformations comprise the coordination to the
alkyne of the electrophilic metal allowing for reactions with a variety of nucleophiles.
We studied the reactivity of alkynylcyclopropanes with rigid structures towards gold
catalysts. First, we discovered a new rearrangement of 1,5-enynes 1 towards cyclohexadienes
2,1 and the proposed intermediate was isolated.2 Moreover, alkynylcyclopropanes 3 bearing a
spiro moiety could be selectively converted into various compounds via 1,5-hydride transfer.3
Alternatively, we studied the ability of inexpensive and low-toxic metals as an alternative to
precious metals (Au, Pt, Rh, Ir). Thus, we reported the use of zinc catalysts for the activation
of enynones 7 to generate furyl zinc carbenes in a catalytic manner. We took advantage of this
approach for the development of various unprecedented zinc-catalyzed reactions.4
Scheme 1
1 J. Barluenga, E. Tudela, R. Vicente, A. Ballesteros, M. Tomás, Angew. Chem. Int. Ed. 2011, 50, 2107.
2 E. Tudela, J. González, R. Vicente, J. Santamaría, M. A. Rodríguez, A. Ballesteros, Angew. Chem. Int. Ed.
2014, 53, DOI: 10.1002/anie.201407055.
3 J. Barluenga, R. Sigüeiro, R. Vicente, A. Ballesteros, M. Tomás, M. A. Rodríguez, Angew. Chem. Int. Ed.
2012, 51, 10377.
4 (a) R. Vicente, J. González, L. Riesgo, J. González, L. A. López, Angew. Chem. Int. Ed. 2012, 51, 8063. (b)
J. González, J. González, C. Pérez-Calleja, L. A. López, R. Vicente, Angew. Chem. Int. Ed. 2013, 52, 5853.
(c) J. González, L. A. López, R. Vicente, Chem. Commun. 2014, 50, 8536.
Bilbao, 4-7 Noviembre 2014
Juan José Cid Martín (Madrid, 1980) se licenció (2002) y doctoró en Químicas (2008) en la
Universidad Autónoma de Madrid bajo la dirección del Prof. Tomás Torres, trabajando en la
síntesis y estudio de sistemas poliméricos y moleculares dador/aceptor para aplicaciones en
células solares orgánicas y de tipo Grätzel (Nanoscience and Molecular Materials Research
Group). Tras un breve periodo en el mismo grupo, se trasladó a Estrasburgo (Francia),
primero al grupo "Laboratoire de Chimie des Matériaux Moléculaires" (Université de
Strasbourg/CNRS) (2008-2009) del Prof. Jean-François Nierengarten, en el que sintetizó
complejos heterolépticos P^N de cobre(I) para aplicaciones en diodos emisores de luz
(LED's), y después, al grupo "Synthèse et Auto-assemblage Moléculaires et
Supramoléculaires" del Institut Charles Sadron (CNRS) (2009-2011) dirigido por el Prof.
Nicolas Giuseppone, donde llevó a cabo la preparación de materiales optoelectrónicos
inteligentes, ordenados supramolecularmente y sensibles a estímulos externos.
Posteriormente, se incorporó mediante un contrato JAE-Doc al grupo "Síntesis Asimétrica y
Nanosistemas Funcionales" del Instituto de Investigaciones Científicas (IIQ)
(CSIC/Universidad de Sevilla) (2011) en Sevilla, bajo la supervisión del Dr. Noureddine
Khiar y en el que actualmente continúa, vinculado al desarrollo de nanomateriales basados en
azúcares, nanotubos de carbono y grafeno como nanovectores terapéuticos y de diagnóstico
del cáncer.
Publicaciones recientes:
1.
M. Assali, J.-J. Cid, I. Fernández, N. Khiar. "Supramolecular Diversity through Click
Ligation: Switching from Self-Assembled Spherical Nanomicelles to 1D-Tubular
Nanostructures and Tridimensional Gels". Chem Mater. 2013, 25, 4250-4261.
2.
M. Assali, J.-J. Cid, M. Pernía-Leal, M. Muñoz-Bravo, I. Fernández, R. E. Wellinger, N.
Khiar. "Glyconanosomes: Disc-shaped Nanomaterials for the Water Solubilization and
Controlled Delivery of Hydrophobic Molecules". ACS Nano 2013, 7, 2145-2153.
3.
J.-J. Cid, J. Mohanraj, M. Mohankumar, M. Holler, G. Accorsi, L. Brelot, I. Nierengarten,
O. Moudam, A. Keaser, B. Delavaux-Nicot, N. Armaroli, J.-F. Nierengarten. "A Stable and
Strongly Luminescent Dinuclear Cu(I) Helical Complex Prepared from 2diphenylphosphino-6-methylpyridine". Chem Commun. 2013, 49, 859-861.
Bilbao, 4-7 Noviembre 2014
Supramolecular Electronics - From Randomly Self-Assembled
Nanostructures to Addressable Self-Organized Interconnects
Juan José Cid,[†] Emilie Moulin and Nicolas Giuseppone*
SAMS Research Group–icFRC, Institut Charles Sadron CNRS–UPR 22, 23 rue du Loess, BP-84087, 67034
Strasbourg cedex 2, France.
[email protected]
Organic electronics makes up one of the most competitive and growing markets for industry
as a consequence of using flexible, energy friendly, easily processable and cheap components
compatible with downscaling towards nano-devices.1 Within this domain, supramolecular
electronics2 has recently been proposed as a promising mesoscalar approach -between plastic
(μm) and molecular electronics (Å) scales- that takes advantage of self-assembly strategies to
construct and process moldable organic nanowires endowed with “pseudocrystalline”
electroactive key regions, from relatively soft functional objects. In order to implement
supramolecular electronics for technological (opto)electronic applications, additional external
elements should be identified and applied in order to control the optoelectronic properties,
addressabilities and precise disposition/integration thereof in miniaturized electronic devices.
The present communication3 focuses on soft self-assemblies made of small organic molecules
or of short monodisperse oligomers yielding to π-stacked one-dimensional (1D) conducting
nano-objects with high aspect ratio. The supramolecular structures, classified according to
their chemical composition, are interlinked with their conductivity properties and
addressability. Likewise, the most recent and important challenges to improve the
conductivity properties of these π -conjugated systems (processing, casting, and aligning
strategies) are gathered, emphasizing those new methods developed using triarylamine and
external stimuli with which self-organized nanowires are constructed directly within a
metallic circuitry to produce well-positioned interconnects with electrical properties
approaching those of SWCNTs (see Figures below).4
[†] Present Address: Laboratory of Asymmetric Synthesis and Functional Nanosystems, Instituto de
Investigaciones Químicas (IIQ), CSIC-Universidad de Sevilla, C/Américo Vepucio 49, 41092 Seville, Spain.
1 R. D. Miller, E. A. Chandross, Chem. Rev. 2010, 110, 1.
2 E. W. Meijer, A. P. H. J. Schenning, Nature 2002, 419, 353.
3 E. Moulin, J.-J.Cid, N. Giuseppone, Adv. Mater. 2013, 25, 477.
4 V. Faramarzi, F. Niess, E. Moulin, M. Maaloum, J.-F. Dayen, J.-B. Beaufrand, S. Zanettini, B. Doudin, N.
Giuseppone, Nat. Chem. 2012, 4, 485.
Sergio Gonell se licenció en Ciencias Químicas por la Universitat Jaume I de Castellón en el
año 2010, y fue galardonado con el premio extraordinario de licenciatura. En el último año de
licenciatura, realizó una estancia de cuatro meses mediante el programa Erasmus-Practicum,
en el Laboratoire de Chimie de Coordination (LCC) del CNRS de Toulouse (Francia) en el
grupo del Prof. Michel Etienne. En 2011 obtuvo una beca predoctoral FPU del Ministerio de
Educación. Actualmente está realizando su Tesis Doctoral en el grupo de Química
Organometálica y Catálisis Homogénea de la Universitat Jaume I de Castellón bajo la
supervisión del Prof. Eduardo Peris y de la Dra. Macarena Poyatos. Durante este periodo ha
realizado una estancia de cuatro meses en el Institut für anorganiche and analytische chemie
and NRW graduate school of chemistry de Münster (Alemania) en el grupo del Prof.
Ekkehardt Hahn. Su tesis se centra en el diseño y síntesis de ligandos politópicos basados en
carbenos N-heterocíclicos para la obtención de materiales polifuncionales.
Publicaciones destacadas:
1.
S. Gonell, M. Poyatos, J. A. Mata, E. Peris. "Y-Shaped Tris-N-Heterocyclic-Carbene
Ligand for the Preparation of Multifunctional Catalysts of Iridium, Rhodium, and
Palladium". Organometallics 2012, 31, 5606-5614.
2.
S. Gonell, M. Poyatos, E. Peris. "Triphenylene-based tris(N-heterocyclic carbene) ligand:
unexpected catalytic benefits". Angew. Chem. Int. Ed. 2013, 52, 7009-7013.
3.
S. Gonell, R. G. Alabau, M. Poyatos, E. Peris, "Unveiling the stereoelectronic properties of
a triphenylene-based tris N-heterocyclic carbene". Chem. Commun. 2013, 49, 7126-7128.
4.
S. Gonell, M. Poyatos, E. Peris. "Main-chain organometallic microporous polymers
bearing triphenylene-tris(n-heterocyclic carbene)-gold species: catalytic properties". Chem.
Eur. J. 2014, 20, 5746-5751.
Bilbao, 4-7 Noviembre 2014
A Triphenylene Based tris-NHC Ligand: from Discrete Trimetallic Complexes to Mainchain Microporous Organometallic Polymers
Sergio Gonell, Macarena Poyatos and Eduardo Peris*
Dpt. de Química Inorgànica i Orgànica, Universitat Jaume I. Avda. Sos Baynat 12071-Castelló (Spain)
[email protected]
During the last years, N-heterocyclic carbenes (NHCs) have emerged as a very useful type of
ligands for homogeneous catalyst design, due to their topologic and electronic versatility,
combined with a great coordination capability.1 Some bis-NHCs have been used as bridging
ligands to obtain homo- and hetero-bimetallic compounds.2 However, there is only a few
examples of tris-NHC capable of bearing three metals at a fixed distance.3
With the aim of increasing the library of multitopic ligands based on NHCs, we have
synthesized a new tris-NHC ligand with D3h-symmetry which possesses a highly delocalized system (Scheme 1, A).4 This tris-NHC ligand readily coordinates to Au(I), Pd(II)4
and Rh(I)5 fragments. The catalytic activities of the Au and Pd-based complexes have been
compared to those exhibited by complexes bearing a triptycene-based tris-NHC (B) and a
benzimidazolylidene ligand (C) in different reactions.
Furthermore, taking profit from the particular topology of this new ligand, we have also
obtained two types of main-chain microporous organometallic polymers based on gold. Their
catalytic properties in heterogeneous catalyzed reactions will also be discussed.
Scheme 1
We gratefully acknowledge financial support from MEC of Spain (CTQ2011-24055/BQU) and
UJI (P1.1B2011-22). We also would like to thank the Ministerio de Economía y Competitividad
for a fellowship (S.G) and the Ramón y Cajal program (M. P.).
________________________________________________
1
2
3
4
5
Herrmann, W. Angew. Chem. Int. Ed. 1997, 41, 1290.
Mata, J. A.; Hahn, F. E.; Peris, E. Chem. Sci. 2014, 5, 1723.
Williams, K. A.; Bielawski, C. W. Chem. Commun. 2010, 46, 5166.
Gonell, S.; Poyatos, M.; Peris, E. Angew. Chem. Int. Ed. 2013, 52, 7009.
Gonell, S.; Alabau, R. G.; Poyatos, M.; Peris, E. Chem. Commun. 2013, 49, 7126.
Organic Materials: the Effect of Subtle Modifications on Device
Performance
Rocío Ponce Ortiz,a Paula Mayorga Burrezo,a Juan Casado,a J. Teodomiro López Navarrete,a
Xugang Guo,b Nanjia Zhou,b Hui Huang,b Antonio Facchettib and Tobin J. Marksb
a
Departamento de Química Física, Universidad de Málaga. bDepartament of Chemistry, Northwestern
University.
[email protected]
In the search of new high-mobility polymeric semiconductors with good processability and
excellent environmental stability, diverse synthetic strategies have been approached. One of
the most widely used consists in the alternation of donor and acceptor moieties in the
conjugated skeleton, which allows fine tuning of the polymer frontier molecular orbitals. For
organic field effect transistors (OFETs) applications, low-lying HOMOs are essential to resist
air oxidation and thus increase device stability. However, if the HOMO energy is too low, the
resulting barrier to hole injection may compromise the transistor performance. Thus, a
delicate balance between these two effects is needed. Furthermore, high performance
solution-processable materials require the correct selection and positioning of the specific
solubilizing substituents in order to achieve proper HOMO and LUMO energy levels, planar
molecular conformations, close intermolecular π-π stacking, and proper thin film crystallinity.
Following these two combined strategies, diverse polymeric materials with great
performances in both OFETs and solar cells, and having remarkable air stability, have been
synthesized and characterized.1,2 This contribution will analyze how small modifications in
their molecular structures can have a great impact on the device performance.
Scheme 1: an example highlighting the effect of subtle modifications on device performance.
1 (a) Huang, H.; Ponce Ortiz, R.; Chen, Z.; Newman, C.; Usta, H.; Lou, S.; Youn, J., Noh, Y.-Y.; Baeg, K.-J.;
Chen, L. X.; Facchetti, A.; Marks, T. J. J. Am. Chem. Soc. 2012, 134, 10966. (b) Guo, X.; Ponce Ortiz, R.;
Zheng, Y.; Gu, Y.; Noh, Y.-Y.; Baeg, K.-J.; Facchetti, A.; Marks, T. J. J. Am. Chem. Soc. 2011, 133, 1405.
(c) Guo, X.; Ponce Ortiz, R.; Zheng, Y.; Kim, M.-G.; Zhang, S.; Gu, Y.; Lu, G.; Facchetti, A.; Marks, T. J. J.
Am. Chem. Soc. 2011, 133, 13685.
2 Guo, X.; Zhou, N.; Lou, S. J.; Smith, J.; Tice, D. B.; Hennek, J. W.; Ponce Ortiz, R.; López Navarrete, J. T.;
Li, S.; Strzalka, J.; Chen, L. X.; Chang, R. P. H.; Facchetti, A.; Marks, T. J. Nature Photonics 2013, 7, 825.
Bilbao, 4-7 Noviembre 2014
New Reaction Partners for Photoinduced, Copper-Catalyzed
Cross-Couplings
José María Muñoz-Molina, Jonas C. Peters, and Gregory C. Fu
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California,
91125, United States
[email protected]
Carbon-heteroatom bond-forming reactions, mediated by a stoichiometric copper reagent at
elevated temp. (>180 °C), were first described by Ullmann at the beginning of the past
century.1 Recent advances in catalytic Ullmann-type cross-couplings make these bondforming processes powerful tools for organic synthesis.2 Our group has recently reported that
photoinduced, copper-catalyzed cross-coupling of carbazole with aryl or alkyl halides can be
achieved under unusually mild conditions.3
In this contribution, we present the development of photoinduced, copper-catalyzed C–X
cross-couplings (X = N, O) as a methodologically simple, mild approach to Ullmann-type
bond constructions.
Scheme 1: photoinduced, copper-catalyzed C–N and C–O bond formation.
Acknowledgments: We thank Gordon and Betty Moore Foundation (grant to J.C.P.), and
Council for International Exchange of Scholars (Fulbright Scholar award to J.M.M.-M.).
1 (a) Ullmann, F. Chem. Ber. 1903, 36, 2382-2384. (b) Ullmann F.; Sponagel, P. Chem. Ber. 1905, 38, 22112212.
2 L. Jiang, S. L. Buchwald, in Metal-Catalyzed Cross-Coupling Reactions, A. De Meijere, F. Diederich, Eds.
(Wiley–VCH, New York, 2004), vol. 2, pp. 699-760.
3 (a) Creutz, S. E.; Lotito, K. J.; Fu, G. C.; Peters, J. C. Science 2012, 338, 647-651. (b) Bissember, A. C.;
Lundgren, R. J.; Creutz, S. E.; Peters, J. C.; Fu, G. C. Angew. Chem., Int. Ed. 2013, 52, 5129-5133.
Sidechain Control of Peptide-based Porous Materials
C. Martí-Gastaldo
Universidad de Valencia, ICMol, 46980, Valencia, Spain
[email protected]
Peptides have recently emerged as naturally occurring linkers for the design of metal organic
frameworks (MOFs) provided their multiple coordination modes, torsional adaptability and
chirality. The use of peptide struts provides unprecedented guest adaptability, 1 modulation of
the framework’s flexibility2 and control over its chemical and mechanical stabilities3 triggered
by suitable choice of the amino acids in the peptidic sequence.
We have recently demonstrated that these porous crystal also show well-ordered porosity
closure controlled by the peptide’s side chain.4 Zn[Gly-Ser]2 evolves from a solvated porous
into a non-porous desolvated state as result of ordered displacive and conformational changes
of the peptide that suppress the void space in response to guest loss. This cooperative closure,
which recalls the folding of proteins, retains order in three-dimensions and is driven by the
hydroxyl groups from the sidechain of the serine residue acting as H-bond donors in the
peptide sequence. This ordered closure is also displayed by multipeptide solid solutions in
which the combination of different sequences of amino acids controls guest response in a nonlinear way
.
Figure 1: porosity closure in Zn(Gly-Ser)2 induced by cooperative folding of the peptide
enabled by conformational change.
1 Rabone, Y. F. Yue, S. Chong, K. Stylianou, J. Bacsa, D. Bradshaw, G. Darling, N. Berry, Y. Khimyak, A.
Ganin, P. Wiper, J. B. Claridge, M. J. Rosseinsky, Science 329, 1053-1057 (2010).
2 C. Martí-Gastaldo, J. E. Warren, K. S. Stylianou, N. O. Flack, M. J. Rosseinsky Angew. Chem. Int. Ed. 51,
11044-11048 (2012).
3 A. P. Katsoulidis, K. Park, D. Antypov, C. Martí-Gastaldo, G. J. Miller, J. E. Warren, C. M. Robertson, F.
Blanc, G. R. Darling, N. G. Berry, J. A. Purton, D. J. Adams, M. J. Rosseinsky Angew. Chem. Int. Ed. 53,
193-198 (2014).
4 C. Martí-Gastaldo , D. Antypov, J. E. Warren, M. E. Briggs, P. A. Chater, P. V. Wiper, G. J. Miller, Y. Z.
Khimyak, G. R. Darling, N. G. Berry, M. J. Rosseinsky Nature Chem. 6, 343-351 (2014).
Bilbao, 4-7 Noviembre 2014
Planar and Twisted Polycyclic Aromatic Hydrocarbons with Pyrazine
Rings
Aurelio Mateo-Alonsoa,b
a
POLYMAT, University of the Basque Country UPV/EHU, Avenida de Tolosa 72, E-20018 Donostia-San
Sebastian, Spain. bIkerbasque, Basque Foundation for Science, Bilbao, Spain
[email protected]
The most recent advances on planar and twisted polycyclic aromatic hydrocarbons with
pyrazine rings, including synthetic routes, optoelectronic properties, self-organising
properties, and potential applications of these molecular materials will be discussed.
Figure 1
________________________________________________
1 G. Tregnago, C. Fléchon, S. Choudhary, C. Gozalvez, A. Mateo-Alonso,* F. Cacialli* “Virtually-pure nearinfrared electroluminescence from exciplexes at polyfluorene/hexaazatrinaphthylene interfaces” Submitted.
2 A. Mateo-Alonso Chem. Soc. Rev., 2014, 43, 6311-6324.
3 S. More, R. Bhosale, and A. Mateo-Alonso Chem. Eur. J., 2014, DOI: 10.1002/chem.201304461.
4 S. More, S. Choudhary, A. Higelin, I. Krossing, M. Melle-Franco and A. Mateo-Alonso Chem. Comm.,
2014, 50, 1976-1979.
5 S. Choudhary, C. Gozalvez, A. Higelin, I. Krossing, M. Melle-Franco and A. Mateo-Alonso Chem. Eur. J.,
2014, 20, 1525-1528.
6 S. More, R. Bhosale, S. Choudhary, A. Mateo-Alonso Org. Lett. 2012, 14, 4170-4173.
7 N. Kulisic, S. More, and A. Mateo-Alonso Chem. Comm. 2011, 47, 514-516.
Design, Chemical Synthesis, and Preclinical Evaluation of QS-21 Saponin
Variants as Improved Vaccine Immunoadjuvants
Alberto Fernández-Tejada, Govind Ragupathi, Samuel J. Danishefsky and David Y. Gin
Department of Molecular Pharmacology and Chemistry, and Department of Medicine; Memorial Sloan
Kettering Cancer Center, 1275 York Avenue, New York, NY 10065,
United States
[email protected], [email protected]
QS-21 is a natural product “adjuvant” that is added to vaccines to improve their efficacy and
potentiate the immune response. It has been used in numerous clinical trials against a variety
of infectious diseases and cancers; however, it suffers from several liabilities, including
heterogeneous composition, chemical instability, dose-limiting toxicity and an enigmatic
mechanism of action.1 To address these challenges, we have designed and chemically
synthesized stable, non-toxic variants of QS-21 that are equally potent and much more
synthetically accessible, enabling the development of novel saponin probes for early
mechanistic investigation. Overall, these extensive chemical and biological studies have
provided critical information about the structural features of QS-21 required for adjuvant
activity, and also important insights into the largely unknown mode of action of this class of
saponin immunoadjuvants.2,3
Scheme 1: chemical structure of the QS-21 natural product adjuvant
A. Fernández-Tejada gratefully acknowledges funding from the European Commission
through a Marie Curie International Outgoing Fellowship.
1 Ragupathi, G.; Gardner, J. R.; Livingston, P. O.; Gin, D. Y. Exp. Rev. Vaccines 2011, 10, 463.
2 Chea, E. K.; Fernández-Tejada, A.; Damani, P.; Adams, M. M.; Gardner, J. R.; Livingston, P. O.; Ragupathi,
G.; Gin, D. Y. J. Am. Chem. Soc. 2012, 134, 13448.
3 Fernández-Tejada, A.; Chea, E. K.; George, C.; Pillarsetty, N.; Gardner, J. R.; Livingston, P. O.; Ragupathi,
G.; Lewis, J. S:, Tan, D. S.; Gin, D. Y. Nat. Chem. 2014, 6, 635.
Bilbao, 4-7 Noviembre 2014
Unsymmetrical Subphthalocyanine Dimers: towards New π-Extended
Curved Structures
Germán Zango,a Christian G. Claessens,a M. Victoria Martínez-Díaz,a and Tomás Torresa,b
a
Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, E-28049
Madrid, Spain. bIMDEA-Nanociencia, c/Faraday, 9, Campus de Cantoblanco, E-28049 Madrid, Spain
[email protected]
Subphthalocyanines (SubPcs)1 are curved aromatic macrocycles, whose geometry is imposed
by the coordination of the three constituent diiminoisoindole units to a central tetrahedral
boron atom. These cone-shaped macrocycles comprise an aromatic 14 π-electron system,
which provides their exceptional photophysical and electrochemical properties as
chromophores in the fields of dyes, nonlinear optics and organic photovoltaics.2,3
Few years ago, subphthalocyanines dimers (SubPc)2 i.e., π-extended system comprising of
two boronsubphthalocyanines units fused through a common benzene ring, were synthesized
and fully characterized.4 These large conjugated molecules present several interesting
properties, as the electronic absorption in the visible region (Q-band) is shifted to the infrared
or near-infrared spectral regions (higher than ~700 nm), and they are among the very few
known examples of curved π-surfaces.
In this work, unsymmetrical subphthalocyanine dimers 1 (Figure 1) have been prepared. The
synthetic route followed is based on the preparation of unsymmetrically substituted orthodicyano SubPcs to be used as extended o-dinitrile precursors of target unsymmetric (SubPcSubPc’) compounds 1. Either electron-donor (t-butyl) or electron withdrawing (Cl) groups
have been introduced on each SubPc half in order to obtain push-pull macrocycles with a
strong asymmetric distribution of π-electrons along the curved aromatic surface.
Figure 1: chemical structure and UV-vis abs. spectrum of unsymmetrical SubPc dimer 1.
1 C. G. Claessens, D. González-Rodríguez, M. S. Rodríguez-Morgade, A. Medina, T. Torres, Chem. Rev.
2014, 114, 2192.
2 G. de la Torre, C. G. Claessens, T. Torres, Chem. Commun. 2007, 2000.
3 G. E. Morse, T. P. Bender, ACS Appl. Mater. Interfaces 2012, 4, 5055.
4 (a) C. G. Claessens, T. Torres, Angew. Chem. Int. Ed. 2002, 41, 2561. (b) T. Fukuda, J. R. Stork, R. J.
Potucek, M. M. Olmstead, B. C. Noll, N. Kobayashi, W. S. Durfee Angew. Chem. Int. Ed. 2002, 41, 2565. (c)
R. S. Iglesias, C. G. Claessens, T. Torres, M. A. Herranz, V. R. Ferro, J. M. García de la Vega, J. Org. Chem.
2007, 72, 2967.
Bilbao, 4-7 Noviembre 2014
Perovskitas Híbridas Halogenadas para Aplicaciones Fotovoltaicas
Emilio J. Juárez-Pérez, Iván Mora-Sero, Juan Bisquert
Grupo de Dispositivos Optoelectrónicos y Fotovoltaicos. Universitat Jaume I, Castellón de laPlana
[email protected]
Recientemente, un nuevo tipo de células fotovoltaicas con material activo basado en una
perovskita ABX3 de halógeno (X), estaño o plomo (B) y catión orgánico (A) ha recibido gran
atención en la comunidad científica debido principalmente a una rápida sucesión de récords
de eficiencia en un corto espacio de tiempo. Actualmente, la máxima eficiencia certificada
obtenida en un dispositivo de laboratorio (área activa pequeña) ha alcanzado eficiencias
cercanas al 18% de conversión de energía superando a todas las tecnologías fotovoltaicas
emergentes hasta ahora estudiadas (celdas orgánicas, de colorante, punto cuántico, etc). En
esta comunicación se expondrá una breve evolución histórica de esta tecnología, las distintas
configuraciones de celda existentes, las composiciones químicas más usadas así como el uso
de la espectroscopia de impedancia para la caracterización de los dispositivos.1
Figura 1
1 (a) Kim, H.-S., Mora-Sero, I., Gonzalez-Pedro, V., Fabregat-Santiago, F., Juárez-Pérez, E. J., Park, N.-G. and
Bisquert, J. Nat. Commun. 2013, 4, 2242. (b) Gonzalez-Pedro, V., Juárez-Pérez, E. J., Arsyad, W.-S., Barea,
E. M., Fabregat-Santiago, F., Mora-Sero, I. and Bisquert, J. Nano Lett. 2014, 14, 888. (c) Juárez-Pérez, E. J.,
Wussler, M., Fabregat-Santiago, F., Lakus-Wollny, K., Mankel, E., Mayer, T., Jaegermann, W. and MoraSero, I. J. Phys. Chem. Lett. 2014, 5, 680. (d) Juárez-Pérez, E. J., Sanchez, R. S., Badia, L., Garcia-Belmonte,
G., Kang, Y. S., Mora-Sero, I. and Bisquert, J. J. Phys. Chem. Lett. 2014, 5, 2390.
Enantioselective Synthetic Approach to the Marine Alkaloids
Madangamines A, C, and D
Celeste Are, Roberto Ballette, Mercedes Amat,* Maria Pérez and Joan Bosch
Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. Joan XXIII s/n, 08028
Barcelona, Spain
[email protected]
Madangamines are a small group of complex pentacyclic alkaloids isolated from marine
sponges of the order Haposclerida. Madangamine A, isolated from Xestospongia ingens by
Andersen in 1994,1 was the first member of this new class of pentacyclic alkaloids and
showed significant in vitro cytotoxicity. Soon afterwards, four new members of this group,
madangamines B-E, were isolated from the same sponge. Structurally, these alkaloids have an
unprecedented skeletal type, characterized by a diazatricyclic core (ABC rings) and two linear
carbon bridges. The peripheral macrocyclic ring D is different in each madangamine, in size
as well as in degree and position of unsaturation, whereas ring E is identical in madangamines
A-E.
In the context of our studies on the enantioselective synthesis of complex piperidinecontaining natural products from phenylglycinol-derived bicyclic lactams, we have developed
a unified strategy to access the variety of alkaloids of this group, in which the formation of the
macrocyclic rings would take place after the construction of the highly functionalized central
core.
Scheme 1
Recently, we have accomplished the enantioselective synthesis of madangamine D, which
represents the first total synthesis of an alkaloid of the madangamine group, 2 and we are
currently studying the construction of the D-ring of more complex members of this family,
madangamines A and C. By the final assembly of the macrocyclic ring E we could complete
the enantioselective synthesis of other members of this group of alkaloids.
Acknowledgment: Financial support from the MICINN, Spain (CTQ2012-35250). Thanks are
also due to PharmaMar S.A. (Madrid) for the cytotoxicity assays.
1 Kong, F.; Andersen, R. J.; Allen, T. M. J. Am. Chem. Soc. 1994, 116, 6007-6008.
2 Ballette, R.; Pérez, M.; Proto, S.; Amat, M.; and Bosch, J. Angew. Chem. Int. Ed. 2014, 53, 6202-6205
Bilbao, 4-7 Noviembre 2014
Argentofilia como Fuerza de Asociación Esencial en un Sistema Dinámico
“Host-Guest” (catión – catión): [Ag(acetonitrilo)2]+ ⊂ [Ag2(bis-NHC)2]2+
Alba Vellé, Andrea Cebollada, Manuel Iglesias, Pablo J. Sanz Miguel
Departamento de Química Inorgánica, ISQCH, Universidad de Zaragoza-CSIC, 50009 Zaragoza
[email protected], [email protected]
La optimización de los sistemas Host-Guest genera un gran interés en muchos campos de
estudio de la Química tradicional y moderna. En la estabilización de este tipo de sistemas
(artificiales y naturales), las interacciones no covalentes juegan un papel fundamental. Nuestra
investigación se centra en construcciones metálicas capaces de alojar pequeñas moléculas,
interaccionar con DNA, o formar enlaces metalofílicos.
Dentro de esta línea, los sistemas Host-Guest formados por complejos de carbenos Nheterocíclicos (NHC) probablemente sean los menos estudiados. Este tipo de ligandos se
comportan como buenos σ-dadores y tienen la capacidad de estabilizar metales en alto estado
de oxidación. De hecho, parece razonable afirmar que la capacidad metalofílica de metales
enriquecidos electrónicamente pueda verse incrementada.
En este trabajo presentamos el sistema [Ag(CH3CN)2]+ ⊂ [Ag2(BisMeOEtIm)2]2+
(BisMeOEtIm = metilenebis(N-2-metoxietil)-imidazol-2-ilideno),1 en el que el anfitrión
[Ag2(BisMeOEtIm)2]2+ aloja el huésped [Ag(CH3CN)2]+. En estado sólido, las interacciones
Ag···Ag constituyen el único “pegamento” entre ambos cationes, superando la inherente
repulsión electrostática. Este caso representa el primer ejemplo de argentofilia no soportada
por la ayuda de un ligando.
Asimismo, encontramos evidencias de este tipo de interacciones Ag···Ag en disolución (1H
NMR), que pueden ser postuladas como una etapa inicial en los mecanismos de
transmetalación, con los centros metálicos directamente implicados en esta transferencia.2
Figura. 1: Formación del Sistema “Host-Guest” [Ag(CH3CN)2]+ ⊂ [Ag2(BisMeOEtIm)2]2+.
Agradecemos la financiación al Ministerio de Economía y Competitividad de España
(Programa “Ramon y Cajal” (P.J.S.M) y CTQ2011-27593).
1 A. Vellé, A. Cebollada, M. Iglesias, P. J. Sanz Miguel, Inorg. Chem. 2014, DOI: 10.1021/ic501715h.
2 A. Vellé, A. Cebollada, M. Iglesias, P. J. Sanz Miguel, resultados sin publicar.
Silicon Particles as Trojan Horses for Potential Cancer Therapy
Susana Alvarez,a Roberto Fenollosa,b Eduardo Garcia-Rico,c Rosana Alvarez,a Xiang Yu,d
Isabel Rodriguez,b Susana Carregal-Romero,d Carlos Villanueva,e Manuel Garcia-Algar,f Pilar
Rivera-Gil,e Angel R. de Lera,c,* Wolfgang J. Parakd,* Francisco Meseguerb,* Ramón A.
Alvarez-Puebla,f,g,*
a
IBIV (instituto de biomedicina de Vigo), Departamento química orgánica. Universidade de Vigo. 36310
Spain. b Centro de Tecnologías Físicas, Unidad Asociada ICMM/CSIC-UPV, Universidad Politécnica de
Valencia, Spain. cServicio de Oncología, Hospital Universitario Madrid-Torrelodones, 28250,Madrid, Spain.
d
Fachbereich Physik, Philipps Universität Marburg, Marburg, 35037 Germany. eMedcomtech SA. Barcelona,
08840 Spain. fDepartamento de Química Física e Inorgánica, Universitat Rovira i Virgili and Centro de
Tecnología Química de Catalunya, Tarragona, Spain. gICREA, Passeig Lluís Companys 23, 08010 Barcelona,
Spain
[email protected]
Cancer is the second cause of death worldwilde. Nanoparticles have shown a great potential
for drug delivery and cancer treatment1. Porous silicon particles (PSiPs) have extensively
been used as drug delivery systems by loading them with chemical species for disease
treatment because of their excellent biocompatibility2 and biodegradability3 properties.
Herein we demonstrate that PSiPs can be used themselves to efficiently and selectively kill
cancer cells and without any external trigger. It is well known from silicon producers that
silicon is characterized by a low reduction potential, which in the case of PSiPs promotes
explosive oxidation reactions with energy yield exceeding that of Trinitrotoluene (TNT). The
functionalization of the silica layer with sugars prevents it from being soluble, the
glucopyranoside selected was 2-acetamido-2-deoxy--D-glucopyranosyloxyacetic acid.
Figure 1
By further functionalization with an appropriate antibody (HER-2), it is possible to increase
their bioaccumulation inside the selected cells. Once internalized into the cells, the sugar is
enzymatically degraded, exposing the soluble silica surfaces to water and promoting the
violent reaction of silicon, thus killing the target cell. Further, this explosive reaction yields
soluble biocompatible residues, easily excretable by urine.
1 (a) Tasciotti et al. Nat. Nano, 2008, 3, 151-157. (b) Park, J.-H. et al, Nat mater, 2009, 8, 331-336
2 Canham, L.T., Adv. Mater., 1995, 7, 1033-1037
3 Popplewell, J.F., J. Inorg. Biochem., 1998, 69, 177-180
Bilbao, 4-7 Noviembre 2014
Evolution of three New Generations of Densely Substituted Unnatural
Proline Organocatalysts
Mª de Gracia Retamosa, Andrea Ruiz-Olalla, Maddalen Agirre and Fernando P. Cossío*
Organic Chemistry Department I, University of the Basque Country (UPV/EHU) Joxe Mari Korta Building
Avda. Tolosa 72, and International Physics Center (DIPC), P.K. 1072, 20018, Donostia – San Sebastián, Spain
[email protected]
Recently, our group has developed an efficient methodology via (3+2) cycloaddition,1
hydrolysis, hydrogenation and peptide coupling to synthesize densely substituted unnatural Land D-Proline derivatives 1, 2 and 3. Encouraged by the efficiency of Proline-based
organocatalysts in several C-C bond transformations, these novel densely substituted
pyrrolidines have been used as organocatalysts in aldol, Michael reactions.2 Aside these
previously known reactions, we have discovered a catalytic cyclization promoted by several
organocatalysts 3. In this communication, we present our results on the structure/activity
relationship of organocatalysts 1-3.
Figure 1
Financial support by the Ministerio de Economia y Competitividad (MINECO) of Spain
(project CTQ2010-16959) and from the Basque Government (Grupos Consolidados IT67313) is acknowledged.
1 (a) Conde, E.; Bello, D.; de Cózar, A.; Sánchez, M.; Vázquez, M. A.; Cossío, F. P. Chem. Sci. 2012, 3, 14861491. (b) Retamosa, M.G.; de Cózar, A.; Sánchez, M.; Miranda, J.I.; Sansano, J.M.; Castelló, L.M.; Nájera,
C.; Jiménez, A.I.; Sayago, F.J.; Cativiela, C., Cossío, F.P., Submitted. (c) Ruiz-Olalla, A.; Retamosa, M. G.;
Cossío, F. P. Submitted.
2 (a) Bisai V.; Bisai A.; Singh, V. K.Tetrahedron, 2012, 68, 4541-4580. (b) Trost, B. M.; Brindle C. S.Chem.
Soc. Rev. 2010, 39, 1600-1632. (c) Xu, L. W.; Luo, J.; Lu, Y. Chem. Comm. 2009, 1807-1821. (d) Vicario, J.
L.; Badía, D.; Carrillo, L.; Reyes, E., Organocatalytic Enantioselective Conjugate Additions Reactions, RSC
Publishing: Cambridge UK 2010
Synthesis, Characterization and Thin Film Processability of Up-Conversion
Particles for their Use in Photovoltaics
Francisco Gonell, Beatriz Julián-López*
Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, 12071 Castelló, Spain
[email protected]
Solar energy conversion constitutes one of the most important scientific and technological
targets of the 21st century to ensure supply on the terawatt scale. Actual devices only take
profit of the ultraviolet and visible part of the solar spectra, losing energy in the sub-bandgap
photons region. In this context, the use of lanthanide doped up-conversion (UC) phosphors,
which are able to transform infrared photons to visible radiation, constitutes a promising
strategy to optimize the spectral match between the incident solar radiation and the absorption
properties of semiconductor materials employed for photovoltaic and photoelectrochemical
devices.
In the first part of the present work we present an innovative family of transparent UC hybrid
materials based on polydimethylsiloxane (PDMS) processed as thin film. The nanocomposite
is constituted by PDMS chain crosslinked with amorphous metal-oxo nanodomains (MxOy
with M: Ti, Zr, Nb, Ta)1 and includes small crystalline Er or Tm, Yb-doped NaYF4
nanoparticles homogeneously distributed in the hybrid.
In the second part we demonstrate that the upcoversion properties of rare-earth doped oxide
nanoparticles (Er0,04Yb0,1Y1,86O3) synthesized with a simple homogeneous co-precipitation
method can be harnessed to produce photocurrent with sub-bandgap photons in
heterostructured TiO2/CdS photoanodes for H2 generation. Furthermore, these up-converting
nanoparticles exhibit remarkable stability, providing some key features for large scale
development.
a)
b)
2
5
7x10

297,5 W/cm
2
265,6 W/cm
2
226,8 W/cm
2
181,0 W/cm
2
128,2 W/cm
2
99,3 W/cm
2
68,6 W/cm
2
55,8 W/cm
2
42,8 W/cm
2
29,5 W/cm
2
15,9 W/cm

G4 H6
5
6x10
5
5
4x10


G4 F4


F3 H6
5

D 2 F 4
3x10
5
2x10
400
500


D 2 H 4


0


D 2 H 6
5
1x10
D 2 H 5

Intensity (a.u.)
5x10
600
700
Wavelength (nm)
Figure 1: a) Emission spectra of the PDMS: NaYF4 (2%Yb, 20% Yb) upon
excitation at 980 nm b) Scanning electron micrograph of Y2O3 (2%Er, 5%Yb)
1 B. Julian, C. Gervais, E. Cordoncillo, P. Escribano, F. Babonneau, C. Sanchez, Chem. Mater. 2003, 15 30263034.
Bilbao, 4-7 Noviembre 2014
Aminocatalytic Approach to the Formation of C=N Bond
Sara Morales, Fernando G. Guijarro, José Luis García Ruano and M. Belén Cid
Department of Organic Chemistry, University Autónoma of Madrid, Cantoblanco 28049, Madrid, Spain
[email protected]
The formation of the C=N bond by condensation of C=O and NH2 groups has been a priority
in organic synthesis mainly due to the relevance of imines and amines in the fields of
chemistry and biology. Moreover, imines are versatile electrophiles that give rise to nitrogencontaining compounds, which are widely distributed in nature and have many important
pharmacological activities.
Based on the application of the concept of nucleophilic catalysis, we have developed a general
and efficient biomimetic approach for the synthesis of aldimines from aldehydes and amines
in the presence of pyrrolidine as catalyst.1 These unprecedented reactions, occurring via
iminium intermediate, have been performed with a variety of N-nucleophiles as NH2SOR,
NH2SO2R, NH2P(O)Ph2 (Scheme 1A).
Scheme 1
Likewise, pyrrolidine allowed the efficient preparation of a wide variety of nitrones using Nsubstituted hydroxylamine hydrochlorides under very mild conditions (Scheme 1B).2
Mechanistic investigation based on NMR experiments and DFT calculations supports the
iminium intermediate I.
Both procedures can be performed with aromatic, heteroaromatic, unsaturated and aliphatic
aldehydes, proceeding with outstanding yields in the absence of acids and metals under safe,
simple and environmentally friendly conditions and minimum experimental manipulation. We
considered this strategy competes with other classical approaches to prepare aldimines and
nitrones.
We thank the Spanish Government (CTQ-2012-35957) and Comunidad Autónoma de Madrid
(S2009/PPQ-1634) for financial support. SM thanks the Spanish Ministry of Economy and
Competitiveness for a predoctoral fellowship (FPI).
1 Morales, S.; Guijarro, F.G.; García Ruano,* J.L.; Cid,*M. B. J. Am. Chem. Soc. 2014, 136, 1082–1089.
2 Morales, S.; Guijarro, F.G.; García Ruano, J.L.; Cid,*M. B. manuscript under preparation.
Teobromina como Inhibidor de la Cristalización del Ácido Úrico y su
Potencial Aplicación en el Tratamiento de Litiasis Renal Úrica
Adrián Rodríguez, Fèlix Grases y Antonia Costa-Bauza
Instituto Universitario de Investigación en Ciencias de la Salud (IUNICS). Departamento de Química.
Universitat de les Illes Balears. Cra. Valldemossa, km 7.5
[email protected]
La litiasis renal por ácido úrico afecta aproximadamente a un 10% de los pacientes litiásicos1.
Hasta la fecha, no se conoce ningún inhibidor de la cristalización del ácido úrico con
aplicación terapéutica, por lo que su tratamiento se basa en la administración de basificantes
urinarios y, en caso de hiperuricemia, la administración de alopurinol.
Por su parte la teobromina, cuya estructura química es similar al ácido úrico, es una
dimetilxantina presente en cantidades importantes en el cacao2. En este trabajo, describimos la
teobromina como un potente inhibidor de la cristalización del ácido úrico.
Utilizando un método turbidimétrico, hemos comprobado que la teobromina retrasa el tiempo
de inducción de la cristalización del ácido úrico en orina sintética, y por lo tanto actúa como
un inhibidor de la nucleación del ácido úrico. Este retraso en el tiempo de inducción depende,
por una parte, de la concentración de teobromina, y por la otra del pH. Los cristales obtenidos
se filtraron y se observaron mediante microscopía electrónica de barrido. Las imágenes
revelaron que la presencia de teobromina cambia la morfología de los cristales de ácido úrico,
formándose cristales más delgados y alargados (imagen 1).
Para acabar, se realizó un experimento en flujo, donde se hizo pasar una disolución de ácido
úrico en orina sintética por una pequeña cámara que contenía fragmentos de cálculos de ácido
úrico obtenidos por litotricia extracorpórea de un mismo paciente. Tras 48 horas, los
fragmentos se secaron y se pesaron. Los resultaron mostraron claramente que, a medida que
aumentaba la concentración de teobromina en la orina sintética, los fragmentos
experimentaban un menor aumento de peso, demostrándose así que la teobromina actúa
también como un inhibidor del crecimiento cristalino.
A
B
Imagen 1. Cristales de ácido úrico obtenidos en orina sintética, (A) en
ausencia de teobromina, (B) en presencia de 20 mg/L de teobromina
Agradecimientos: Conselleria d’Educació, Cultura i Universitat (Illes Balears) por la beca FPI
1570/2013; fondos FEDER y FSE.
1 Grases F, Conte A, March JG, et. al. Int Urol Nephrol 1994 26:145-150.
2 Craig WJ, Nguyen TT. J Food Sci 2006 49:302-303
Bilbao, 4-7 Noviembre 2014
Ni-catalyzed Reductive Couplings via C−O Bond Activation
Arkaitz Correaa and Ruben Martinb*
a
ICIQ, Av. Països Catalans 16, 43007, Tarragona; ICREA, Passeig Lluïs Companys, 23, 08010, Barcelona.
b
UPV/EHU, Joxe Mari Korta, Av. Tolosa 72, 20018, Donostia-San Sebastián.
[email protected]
The recent years have witnessed a renaissance in the field of C–O bond activation and C–O
electrophiles have lately emerged as versatile, cost-efficient and sustainable alternatives to the
use of organic halides in the cross-coupling arena.1 Despite remarkable advances, their use in
metal-catalyzed reductive events is relatively scarce.2 We report herein the discovery of novel
Ni-catalyzed reductive carboxylation3 and amidation4 events with CO2 and isocyanates,
respectively (Scheme 1). These protocols are applicable for both of C(sp2)− and C(sp3)−O
electrophiles and constitute practical, user-friendly and operationally-simple strategies for the
assembly of a wide range of synthetically relevant carboxylic acids and benzamides. Such
formal umpolung reactions provide innovative bond disconnection, not apparent at first sight,
which complement existing methodologies based on functional group manipulation or
involving well-defined and air-sensitive organometallics.
Scheme 1. Ni-catalyzed reductive couplings via C−O bond activation.
Acknowledgements. We thank ICIQ Foundation, the European Research Council (ERC277883) and MINECO (CTQ2012-34054) for financial support. A.C. thanks MINECO for a
RyC fellowship.
1 (a) Cornella, J.; Zarate, C.; Martin, R. Chem. Soc. Rev. 2014, DOI: 10.1039/C4CS00206G. (b) Tobisu, M.;
Chatani, N. Top. Organomet. Chem. 2013, 44, 35. (c) Tehetena, M.; Garg, N. K. Org. Process Res. Dev.
2013, 17, 29. (d) Correa, A.; Cornella, J.; Martin, R. Angew. Chem., Int. Ed. 2013, 52, 1878. (e) Rosen, B.
M.; Quasdorf, K. W.; Wilkson, D. A.; Zhang, N.; Resmerita, A.-M.; Garg, N.K.; Percec, B. Chem. Rev. 2011,
111, 1346.
2 (a) Moragas, T.; Correa, A.; Martin, R. Chem Eur. J. 2014, 20, 8242. (b) Knappke, C. E. I.; Grupe, S.;
Gärtner, S.; Corpet, M.; Gosmini, C.; Jacobi von Wangelin, A. Chem. Eur. J. 2014, 20, 6828. (c) Everson, D.
A.; Weix, D. J. J. Org. Chem. 2014, 79, 4793.
3 (a) Correa, A.; León, T.; Martin, R. J. Am. Chem. Soc. 2014, 136, 1062. For related reductive carboxylations
utilizing aryl halides, see: (b) Liu, Y.; Cornella, J.; Martin, R. J. Am. Chem. Soc. 2014, 136, 11212. (c) León,
T.; Correa, A.; Martin, R. J. Am. Chem. Soc. 2013, 135, 1221. (d) Tran-Vu, H.; Daugulis, O. ACS Catal.
2013, 3, 2417. (e) Fujihara, T.; Nogi, K.; Xu, T.; Terao, J.; Tsuji, Y. J. Am. Chem. Soc. 2012, 134, 9106. (f)
Correa, A.; Martin, R. J. Am. Chem. Soc. 2009, 131, 15974.
4 Correa, A.; Martin, R. J. Am. Chem. Soc. 2014, 136, 7253.
Formation of Micelles and their Hydration in Gas Phase
Iker León, Pedro F. Arnaiz, Jorge González, Imanol Usabiaga, Emilio J. Cocinero and José A.
Fernández
Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU),
Ap. 644, E-48080 Bilbao, Spain
[email protected]
Here we present the first combined spectroscopic and computational study on the formation
of a 1.6 nm micelle containing up to six molecules of propofol. The observed structures
clearly show that formation of a hydrogen bond network conditions the structure of the
micelle, while the non-polar groups arrange is such a way that the rest of non-covalent
interactions are maximized. We observed the critical balance between hydrogen bond
interactions and non-covalent forces in the control of the aggregation process. The work
clearly reflects the importance of multiple weak non-covalent interactions in the final shape of
biological supramolecular structures. Additionally, in a quest for understanding what the
driving forces are for the encapsulation of water in these supramolecular structures we
introduced water molecules in the nano-micelles in a controlled sequential way. Interpretation
of the spectra in the light of high level calculations allowed us to determine the cluster’s
structure and to demonstrate that the trimer of propofol with a water molecule form cyclic
hydrogen-bond networks but, on the other hand, the tetramer is big enough to encapsulate the
water molecule inside its hydrophilic core. Furthermore, these micelles are remarkably stable
highlighting the capability of these micelles to trap water inside.
Scheme 1: formation of a 1.6 nm micelle containing up to six molecules of propofol.
Bilbao, 4-7 Noviembre 2014
Organocatalytic Enantioselective Friedel-Crafts Reaction of Naphthols with
Cyclic Imines
Marc Montesinos-Magraner, Rubén Cantón-Vitoria, Isabel Fernández and José R. Pedro*
Departament de Química Orgànica, Universitat de València, Burjassot, 46100, Spain
[email protected]
The enantioselective addition of aromatic rings to imines, aza-Friedel-Crafts reaction (AFC),
has been extensively studied using indoles and pyrroles as nucleophiles.1 However, the AFC
reaction with naphthols has been less developed maybe due to their lower nucleophilicity. The
first organocatalytic enantioselective additions of 1- and 2-naphthol to tosylimines were
described by Wang and Chimni, respectively.2 Both group employed 6’-OH cinchona
alkaloids as bifunctional catalysts.
Additionally, benzoxathiazine-2,2-dioxides 2 have recently become an interesting electrophile
in several transformations.3 These cyclic imines are an advantageous alternative to
tosylimines due to the lower conformational mobility and the lack of E/Z isomerization of the
double bond. Moreover, the resulting sulfamidate moiety is a versatile group that can be
transformed in different functional groups.3a,4
In this communication we present the enantioselective addition of naphthols 1 to
benzoxathiazine-2,2-dioxides 2 catalyzed by a 6’-OH cinchona alkaloid, obtaining the
corresponding sulfamidates 3 in good yields and enantioselectivities. We also describe some
synthetic applications of the obtained products.
Scheme 1
Financial support from the Ministerio de Ciencia e Innovación and FEDER (CTQ 200913083) and from Generalitat Valenciana (ACOMP/2012/212 and ISIC/2012/001) is
acknowledged. M.M. thanks the Universitat de València for a pre-doctoral grant.
1 (a) Jia, Y.- X.; Xie, J.- H.; Duan, H.- F.; Wang, L.- X.; Zhou, Q.- L. Org. Lett. 2006, 8, 1621-1624. (b) Wang,
Y.- Q.; Song, J.; Hong, R.; Li, H.; Deng, L. J. Am. Chem. Soc. 2006, 128, 8156-8157. (c) Li, G.; Rowland, G.
B.; Rowland, E. B.; Antilla, J. C. Org. Lett. 2007, 9, 4065-4068.
2 a) Liu, G. ; Zhang, S.; Li, H.; Zhang, T.; Wang, W. Org. Lett. 2011, 13, 828-831. (b) Chauhan, P.; Chimni,
S. S. Eur. J. Org. Chem. 2011, 1636-1640.
3 (a) Luo, Y.; Carnell, A. J.; Lam, H. W.; Angew. Chem. Int. Ed. 2012, 51, 6762-6766. (b) Luo, Y.; Hepburn,
H. B.; Chotsaeng, N.; Lam, H. W. Angew. Chem. Int. Ed. 2012, 51, 8309-8313. (c) Wang, H.; Jiang, T.; Xu,
M.-H. J. Am. Chem. Soc. 2013, 135, 971-974. (d) Liu, Y.; Kang, T.-R.; Liu, Q.-Z.; Chen, L.-M.; Wang, Y.C.; Liu, J.; Xie, Y.-M.; Yang, J.-L.; He, L. Org. Lett. 2013, 15, 6090-6093.
4 (a) Lorion, M.; Agouridas, V.; Couture, A.; Deniau, E.; Grandclaudon P. Org. Lett. 2010, 12, 1356-1359. (b)
When, P. M.; Du Bois, J. Org. Lett. 2005, 7, 4685-4688.
Controlling the Translational Motion in Hydrogen-Bonded Rotaxanes by
Molecular Recognition Events
Alberto Martínez-Cuezva, José Berná, Raúl A. Orenes, Aurelia Pastor, Mateo Alajarín
Departamento de Química Orgánica, Facultad de Química, Campus de Excelencia Internacional Regional
"Campus Mare Nostrum", Universidad de Murcia, 30100 Murcia, Spain
[email protected]
Controlling motion in interlocked molecular architectures has been a trending topic during the
last decade for the scientific community1 and, mainly, for researchers interested on the
modelization of the biological machinery and the development of stimuli-responsive
molecular devices.2
External control of the translational motion of the macrocycle can be achieved by using
different stimuli, such as chemical, electrochemical or photochemical inputs. In this
communication we report that the addition of small molecules, e. g. barbital or Nhexylthymine, restrict this motion. The di(acylamino)pyridine stations interact with the new
molecules, confining the movement of the macrocycle to the aliphatic chain. The addition of a
Hamilton-type receptor, specially designed for barbital trapping, allows the recovery of the
initial ring dynamics.3
Figure 1
This work has been funded by the European Union Seventh Framework Programme-Marie
Curie COFUND (FP7/2007-2013) under UMU Incoming Mobility Programme ACTion (UIMPACT) Grant Agreement 267143, MICINN (Project CTQ2009-12216/BQU) and
Fundación Séneca-CARM (Project 08661/PI/08).
________________________________________________
1. (a) V. Balzani, A. Credi, M. Venturi, From Non-Covalent Assemblies to Molecular Machines, 2011, 159. (b)
J. F. Stoddart, Chem. Soc. Rev. 2009, 38, 1802.
2. (a) E. R. Kay, D. A. Leigh, F. Zerbetto, Angew. Chem. Int. Ed. 2007, 46, 72. (b) J. Berna, M. Alajarin, R.-A.
Orenes, J. Am. Chem. Soc. 2010, 132, 10741.
3. A. Martinez-Cuezva, J. Berna, R.-A. Orenes, A. Pastor, M. Alajarin, Angew. Chem. Int. Ed. 2014, 53, 6762.
Bilbao, 4-7 Noviembre 2014
Deep Eutectic Solvents (DESs): Green and Biorenewable Reaction Media
for Metal-Catalyzed Organic Reactions
Joaquín García-Alvarez,* María J. Rodríguez-Álvarez and Cristian Vidal
Laboratorio de Compuestos Organometálicos y Catálisis (Unidad Asociada al CSIC), Departamento de
Química Orgánica e Inorgánica, Facultad de Química, Universidad de Oviedo, C/ Julián Clavería, nº 8, 33006,
Oviedo (Spain).
[email protected]
During the last few decades a huge amount of effort has been dedicated to the development of
catalytic processes in agreement with the 12 Principles of the so called Green Chemistry. 1 In
this sense, one of the crucial points in realizing a catalytic Green Chemical process involve
the choice of a safe, non-toxic and cheap solvent, like for example, Deep Eutectic Solvents
[DESs, formed by combining a hydrogen bond donor (i.e. glycerol or urea) with a simple
halide salt (choline chloride)].2 Although DESs have been already explored in a variety of
applications including metal deposition, purification of biodiesel, biotransformations and
different synthetic processes, their use in metal-mediated organic reactions has been barely
noticed.3 Together with the choice of a green solvent, it is also desirable that the reactions
proceed with energy efficiency (if possible, synthetic methods should be conducted at
ambient temperature), in high yields, as selective and specific processes, under aerobic
conditions and maximizing the atom economy. In this regard, the metal-catalyzed
cycloisomerization of γ-alkynoic acids conducted in DESs and at room temperature fulfils the
principles of Green Chemistry, providing an efficient entry to enol-lactones, a class of densely
functionalized small heterocycles.
Thus, in this communication, we will present a new family of simple and versatile
iminophosphorane-Au(I) complexes 3,4a-b as selective catalysts for the rapid and efficient
cycloisomerization of both terminal and internal γ-alkynoic acids (1) into their corresponding
enol-lactones (2) in DESs, at room temperature and under air. In addition, the catalytic system
could be also recycled in five consecutive runs.
Scheme 1
1 Anastas, P. T.; Warner, J. C. In Green Chemistry Theory and Practice, Oxford University Press, 1998
2 García-Álvarez, J. Deep Eutectic Solvents and Their Applications as New Green and Biorenewable Reaction
Media, In Handbook of Solvents, Vol. 2, 2nd Edition: Use, Health, and Environment, (Wypych, G. Ed.)
ChemTec Publishing, Toronto, 2014.
3 (a) Vidal, C.; Suárez, F. J.; García-Álvarez, J. Catal. Commun. 2014, 44, 76. (b) Vidal, C.; García-Álvarez,
J.; Hernán-Gómez, A.; Kennedy, A. R.; Hevia, E. Angew. Chem. Int. Ed. 2014, 53, 5969.
Synthesis of Cyclic 1,2-Amino Alcohols via Organocatalytic
Enantioselective [4+2] Cycloaddition
Iker Riaño, Jose L. Vicario, Luisa Carrillo, Efraím Reyes and Uxue Uria
Department of Organic Chemistry II, Faculty of Science and Technology, University of the Basque Country
(UPV/EHU), P. O. Box 644, 48080 Bilbao (Spain)
[email protected]
The [4+2] cycloaddition1 has become one of the most powerful tools for the construction of
polyfunctional 6-membered carbocycles in a single step. The preparation of many
pharmaceuticals is based on this type of reactions and many applications have also been found
in total synthesis of natural products.2 For this reason, the development of new approaches in
an asymmetric version is a field of great interest.
In this context, we describe herein an organocatalytic [4+2] cycloaddition between α,βunsaturated sulfonyl imines and α,β-unsaturated aldehydes promoted by chiral amine as
catalyst under iminium ion activation (Scheme 1).
Scheme 1
This stepwise reaction provides straightforward access to polycyclic frameworks in a
stereocontrolled way with the generation of five contiguous stereocenters. The interest of this
methodology has been demonstrated by the transformation of these adducts into the
corresponding cyclic 1,2-amino alcohols, using a well-known procedure, which can play
different roles in organic chemistry such as ligand, organocatalyst or chiral auxiliary.3
Acknowledgements: Financial support by the Spanish MICINN (CTQ2011-22790 and Juan
de la Cierva Contract to U.U.), the Basque Government (Grupos IT328-10) and UPV/EHU
(EHUA12/09, UFI QOSYC 11/22 and fellowship to I.R.) is gratefully acknowledged.
Membership in the COST Action CM0905 is also acknowledged.
1 Merino, P.; Marques-Lopez, E.; Tejero, T.; Herrera, R. P. Synthesis 2010, 1, 1-26.
2 For a review, see: Nicolaou, K. C.; Snyder, S. A.; Montagnon, T.; Vassilikogiannakis, G. Angew. Chem. Int.
Ed. 2002, 41, 1668-1698.
3 For selected reviews, see: (a) Della Sala, G.; Russo, A.; Lattanzi, A. Curr. Org. Chem. 2011, 15, 2147-2183;
(b) Anaya de Parrodi, C.; Juaristi, E. Synlett 2006, 17, 2699-2715; (c) Ager, D. J.; Prakash, I.; Schaad, D. R.
Chem. Rev. 1996, 96, 835-875.
Bilbao, 4-7 Noviembre 2014
Ring Fluorination Effects on Molecular Water Clusters: the Cases of 2Fluoropyridine, 3-Fluoropyridine and penta-Fluoropyridine. A Rotational
Spectroscopy Study.
Camilla Calabrese,a Qian Gou,a Lorenzo Spada,a Montserrat Vallejo-López,b Assimo Maris,a
Sonia Melandria and Walther Caminatia
a
Dipartimento di Chimica "G. Ciamician”, Università di Bologna, Via Selmi 2, I-40126 Bologna,
Italy. Departamento de Química Física y Química Inorgánica, Universidad de Valladolid, Paseo de Belén, 7.
47011, Valladolid, Spain.
b
[email protected]
The importance of organic fluorinated compounds in science and in everyday life is growing
year after year.1 The effects of fluorination are related to the high electronegativity of this
atom and its polarizability. In general the introduction of a fluorine atom is used in order to
modulate physicochemical properties, like hydrophilicity and lipophilicity, of bio-organic
molecules and functional materials.1,2 Additionally, structural changes can also be related to
the electronic effect of the fluorine atom or to the molecule capability of creating new
hydrogen bonds or non-covalent bonds, having fluorine as acceptor. For this reason we
investigate clusters where a molecule of water is used as a probe to reveal the changes on the
electrostatic potential on the fluorinated compounds.
The experimental conditions are achieved in supersonic expansions using Molecular Beam
Fourier Transform Microwave Spectroscopy technique (MBFTMW).3 The high resolution and
sensitivity of rotational spectroscopy give direct access to the structural arrangement of the
systems, allowing the measurement of bond lengths and angles. Moreover this gas phase
technique allows unveiling subtle structural and dynamical effects usually related to changes
in non-covalent interactions.
The series of clusters studied between different fluorinated pyridines and a molecule of water
are: 2-fluoropyridine-water, 3-fluoropyridine-water and penta-fluoropyridine-water (Figure 1)
complexes. The results clearly show that the introduction of a single fluorine atom into a
molecule already induces significant effects, but as the number of fluorine atoms increases,
such as in the case of penta-fluoropyridine, the system starts to behave as a completely novel
species.4 The perfluorination effect is clearly observable in the penta-fluoropyridine-water
adduct where the water oxygen lone pairs point towards the aromatic ring.
2.808 Å
1.978 Å
157°
3.00 Å
2.015 Å
152.0°
3-FluoroPyridine• • • H2O
83.59°
61.7°
2.753 Å
2-FluoroPyridine • • • H2O
penta-FluoroPyridine• • • H2O
Figure 1: the observed adducts of 2- and 3-fluoropyridine and penta-fluoropyridine
________________________________________________
1 Berger R., Resnati G., Metrangolo P., Weberd E. and Hulliger J. Chem. Soc. Rev. 2011, 40, 3496.
2 (a) K. Müller, C. Faeh, F. Diederich, Science, 2007, 317, 1881. (b) H. Matter, M. Nazar, S. Gussregen, D.W.
Will, H. Schreuder, A., Angew. Chem., 2009, 121, 2955.
3 Caminati W.; Millemaggi A.; Alonso J.L.; Lesarri A.; Lopez J.C. Mata S. Chem. Phys. Lett. 2004, 1, 392.
4 Cametti M., Crousse B., Metrangolo P., Milanicd R., Resnati G. Chem. Soc. Rev. 2012, 41, 31.
Nanoformas de Carbono Electroactivas: Síntesis y Caracterización
Sonia Vela,a Laura Rodriguez,a Carmen Atienzaa y Nazario Martína,b
a
Grupo de Materiales Moleculares, Departamento de Química Orgánica I, Universidad Complutense de
Madrid, 28040 Madrid, España. bIMDEA Nanociencia, Campus Cantoblanco, 28049 Madrid, España.
[email protected]
Los materiales basados en carbono como fullerenos, nanotubos de carbono (CNTs) y grafeno
juegan un papel importante en la ciencia y tecnología de hoy en día, debido a sus propiedades
mecánicas, ópticas y electrónicas. Todos ellos poseen una amplia variedad de aplicaciones en
el campo de la optoelectrónica, dispositivos fotovoltáicos y transistores orgánicos, entre
ellos.1
Sin embargo, uno de los principales problemas de estos materiales basados en carbono,
concretamente CNTs y grafeno, es su difícil manejo debido a su baja solubilidad. Esto
conlleva la disminución del rendimiento global de dicho material e interfiere en sus
propiedades. Por lo tanto, debemos realizar un proceso de modificación química de dichas
estructuras de carbono, para poder manejarlas; dicha funcionalización puede ser (i) covalente,
que presentan como principal desventaja la alteración de las propiedades electrónicas debido a
la modificación en su estructura2 o (ii) funcionalización no-covalente, tales como enlaces de
hidrógeno o interacciones electrostáticas que dependen de parámetros externos como el
disolvente utilizado, la concentración o el pH, pero no afectaría a la estructura de carbono,
conservando intactas sus propiedades electrónicas.3 Sin embargo, la combinación de ambos
tipos de funcionalización puede proporcionar materiales robustos.
De ahí, que en este trabajo nos propusimos la modificación covalente de nanotubos de
carbono de pared sencilla y la unión a través de química no-covalente a una unidad electro
dadora de tipo porfirina. Para ello, llevamos a cabo la funcionalización de los CNTs con un
grupo ácido carboxílico terminal que nos permite anclar supramolecularmente la unidad de
porfirina a través interacciones por enlaces de hidrógeno amidinina-carboxilato. (figura 1)
Esto nos permitirá obtener estructuras electroactivas con aplicaciones en dispositivos
fotovoltaicos.
Figura 1: diada supramolecular
1 Malig, J.; Jux, N.; Guldi, D. M. Acc. Chem. Res., 2013, 46, 53.
2 Rodríguez-Pérez, L.; García, R.; Herranz, M. A.; Martín N. Chem. Eur. J.,2014, 20, 7278 – 7286
3 Garrot, D.; Langlois, B.; Roquelet, C.; Michel, T.; Roussignol, P.; Delalande, C.; Deleporte, E.; Lauret, J.;
Voisin, C. Chemphyschem 2014, 115, 23283
Bilbao, 4-7 Noviembre 2014
Mixed Matrix Membranes for CO2-N2 Separation: Effect of the Si/Al Ratio
of Zeolite Fillers
Ana Fernández-Barquín, Clara Casado-Coterillo, Susana Valencia and Ángel Irabien
Department of Chemical and Biomolecular Engineering, Universidad de Cantabria, Av. Los Castros s/n, 39005
Santander, Cantabria, Spain
[email protected]
A membrane is a selective semipermeable barrier that allows the separation of the
components in a mixture. The ability of membranes to separate efficiently CO2 from other
light gases has received a great deal of attention due to its potential as alternative energyefficient process reducing greenhouse gas emissions.1 However, commercially available
membranes are still in an early stage of development, because of lack of thermal and chemical
stability, and the trade-off between the permeability and selectivity.2 The permeability and
selectivity of membranes should be as high as possible for their efficient use in industrial gas
separation applications.
Poly (1-trimethylsilyl-1-propyne) (PTMSP) is a super glassy polymer with high glass
transition temperature and the highest known gas permeability. However, its permeability is
coupled with low ideal selectivity and decreases rather dramatically with time because of
physical aging. Mixed matrix membranes (MMMs) are composed of a dispersed filler in a
continuous polymer matrix, providing a novel material of synergistic properties of the
components:3 CO2 adsorptive capacity of inorganic crystals and the high permeability and
processability of the polymer. Zeolites are the most common fillers used in mixed matrix
membranes. Zeolites are crystalline aluminosilicates with regular channels where the Si/Al
ratio may be varied to tune up the adsorption of small polar molecules such as CO2.
MMMs prepared from PTMSP and LTA-type zeolites, with different Si/Al ratio: commercial
NaA (Si/Al =1), pure silica ITQ-29 (Si/Al = ∞) and chabazite (Si/Al=5),4 were prepared at
different loadings. The CO2 solubility of the new materials was measured gravimetrically in
the temperature range 298-333 K. As expected, the CO2 solubility in pure polymer and high
Si/Al zeolite-PTMSP MMMs decreases with temperature. When the ITQ-29 zeolite is used as
filler, the CO2 solubility also decreases with the zeolite loading. On the other hand, when the
low silica zeolite, NaA zeolite, is used as filler, it is observed that the CO2 solubility is
improved both with increasing zeolite loading and temperature. This may be attributed to the
lowest CO2 sorption capacity of the hydrophobic pure silica ITQ-29, as compared with other
LTA-type zeolites.4
The Spanish Ministry Economy and Competitiveness (Project CTQ2012-31229) and the
Royal Spanish Society of Chemistry in Cantabria (RSEQ ST-Cantabria), have funded this
research. C.C.C. and A.F.B. also acknowledge the MINECO for the Ramón y Cajal (RYC2011-08550) and FPI postgraduate (BES-2013-064266) research grants, respectively.
1
2
3
4
Haszeldine, R.S. Science, 2009. 325: 1647-1652.
Robeson, L. M. J. Membr. Sci, 2008. 320: 390-400.
Chung, T. S. et al. S. Prog. Polym. Sci. 2007. 32: 483-507.
Palomino, M. et al. Langmuir. 2009. 026(3): 1910–1917.
Nuevas Reacciones de Borilación Catalizadas por Cobre(I): Carboboración
de Alquinos y Alquenos Tensionados
Alejandro Parra, Aurora López, Laura Amenós, Sergio Díaz Tendero, J. L. García Ruano,
Mariola Tortosa
Departamento de Química Orgánica (Módulo-1), Universidad Autónoma de Madrid, Cantoblanco, 28049
Madrid, España
[email protected]
La incorporación de enlaces carbono-boro de manera selectiva se ha perfilado como un
importante reto en los últimos años, ya que éste es considerado como uno de los enlaces más
versátiles en química por su fácil transformación en enlaces tan fundamentales como: C-O, CN, C-C, entre otros.1 En este sentido, las reacciones de borilación catalizadas por cobre, que
generan in situ una especie nucleófila R2B-[Cu]-1 (esquema 1), han emergido como una
herramienta poderosa para efectuar enlaces C-B de manera regio, estereo y, enantioselectiva.2
En esta comunicación se mostrarán los resultados obtenidos en nuestro grupo de investigación
llevados a cabo usando esta metodología. En primer lugar, hemos desarrollado la primera
carboboración de alquinos catalizada por Cu(I) que permite obtener ésteres alquenil
borónicos, precursores directos de olefinas tri- y tetra-sustituidas, de manera totalmente
regioselectiva y con buenos rendimientos (A, esquema 1).3a En segundo lugar, nos hemos
centrado en el estudio de la hidro- y carboboración de alquenos tensionados con una doble
finalidad: a) estudiar la reactividad de alquenos sin grupos no activantes y, que a su vez tienen
un importante valor sintético y, b) establecer una relación entre la tensión del doble enlace y
la reactividad mediante reacciones de competencia, contrastando para ello los resultados con
cálculos teóricos (B, esquema 1).3b
Esquema 1
Agradecimientos: Los autores agradecen la financiación recibida por el gobierno español
(CTQ-2009-12168), a la CAM (“programa AVANCAT CS2009/PPQ-1634”) y, al European
Research Council (ERC-337776). A. P. y M. T agradecen al MICINN por un contrato Juan de
la Cierva y Ramón y Cajal, respectivamente.
1 Hall, D. Boronic Acids: Preparation and Applications in Organic Synthesis and Medicine, Wiley-VCH:
Weinheim, 2005.
2 Para algunas referencias destacadas, véase: (a) Zhang, L.; Cheng, J.; Carry, B.; Hou Z. J. Am. Chem. Soc.
2012, 134, 14314. (b) Matsuda, N.; Hirano, K.; Satoh, T.; Miura, M. J. Am. Chem. Soc. 2013, 135, 4934.
3 (a) Alfaro, R.; Parra, A.; Alem n, J.; García Ruano, J. L.; Tortosa, M. J. Am. Chem. Soc. 2012, 134, 15165.
(b) Parra, A.; López, A.; Amenós, L.; Díaz-Tendero, S.; García Ruano, J. L.; Tortosa, M. Manuscrito en
preparación.
Bilbao, 4-7 Noviembre 2014
Influencia de Ligandos Tioéter Corona y de Grupos Perhalofenilo en la
Estructura y en las Propiedades Ópticas de Complejos con Interacciones
Metalofílicas.
Rocío Donamaría, M. Elena Olmos, Alexander J. Blacke, M. Concepción Gimeno, Tania
Lasanta, Vito Lippolis, J. M. López-de-Luzuriaga, Elena Manso y Miguel Monge.
Grupo de investigación GEIMA, Departamento de Química, Complejo Científico Tecnológico, Universidad de
La Rioja-CISQ, 26004, Logroño, España.
[email protected]
La química de los sistemas supramoleculares heteropolinucleares extendidos construidos a
partir de interacciones secundarias ha atraído gran interés en los últimos años debido a las
interesantes propiedades que presentan, en especial las propiedades ópticas.1 En nuestro grupo
de investigación se ha desarrollado una estrategia ácido-base mediante la reacción de
compuestos de estequiometría NBu4[Au(C6X5)2] con sales de AgI y TlI, mediante la cual se
han sintetizado un gran número de estos sistemas.2
En este contexto, estudiamos la reactividad de los precursores básicos [Au(C6X5)2]- (X = F,
Cl) frente a las sales ácidas Ag(OClO3) o Tl(PF6) en presencia de ligandos polidentados Sdadores, como el 1,4,7-tritiaciclononano ([9]aneS3), 1,4,8,11-tetratiociclotetradecano
([14]aneS4) y 1,4,7,10,13,16,19,22-octatiociclooctacosano ([24]aneS8). Así, obtuvimos
compuestos heteronucleares AuI/MI (M = Ag, Tl)
de diferente estequiometría y
comportamiento óptico. Su luminiscencia depende de un gran número de factores a estudiar:
la naturaleza del heterometal, la disposición estructural de los metales y su entorno, la
naturaleza de los ligandos S-dadores y de los grupos arilo unidos a los centros de AuI.
Llevamos a cabo cálculos teóricos DFT y TD-DFT con el objeto de estudiar el origen de las
propiedades ópticas y los diferentes parámetros que pueden influir en éstas.
Imagen 1: Estudio de las propiedades ópticas del compuesto [{Au(C6Cl5)2}Ag([14]aneS4)].
Agradecimientos: D.G.I.(MEC)/FEDER (nº de proyecto: CTQ2013-48635-C2-2-P) por
financiar la investigación, y al CESGA-Centro de Supercomputación de Galicia por los
recursos informáticos.
1 Ver por ejemplo: (a) Pyykkö, P; Chem Rev 1997, 97, 597. (b) López-de-Luzuriaga, J.M.; Laguna, A.; WileyVCH, Weinheim, 2008, 347-401.
2 Ver por ejemplo: Fernández, E.J.; López-de-Luzuriaga, J.M.; Monge, M.; Olmos, M.E.; Puelles, R.C.;
Laguna, A.; Mohammed, A.A.; Fackler, Jr., J.P., Inorg. Chem. 2008, 47, 8069.
Nanoreactors for Simultaneous Remote Thermal-Activation and Optical
Monitoring of Chemical Reactions
Belén Vaz,a Carmen Vázquez Vázquez,b Vincenzo Giannini,c Moisés Pérez Lorenzo,b Ramón
A. Álvarez Puebla,d,e Miguel A. Correa-Duarte.b
a
Department of Organic Chemistry and bDepartment of Physical Chemistry, Universidade de Vigo, 36310 Vigo,
Spain. cDepartment of Physics, Imperial College London, London SW7 2AZ, U.K. dUniversitat Rovira i Virgili
and Centro de Tecnología Química de Catalunya, Carrer de Marcel·lí Domingo s/n, 43007 Tarragona, Spain.
eICREA, Passeig Lluís Companys 23, 08010 Barcelona, Spain.
[email protected]
The unprecedented ability of plasmon-resonant metallic structures to concentrate light at the
nanometer scale1 has propelled their use in a vast array of photonics technologies
(plasmonics) and research endeavors. We report herein the design of plasmonic hollow
nanoreactors (PNR) capable of concentrating light at the nanometer scale for the simultaneous
performance and optical monitoring of thermally activated reactions. These reactors feature
the encapsulation of plasmonic nanoparticles on the inner walls of a mesoporous silica
capsule. A Diels−Alder cycloaddition reaction was carried out in the inner cavities of these
nanoreactors to evidence their efficacy.2
Figure 1: schematic cross-section view of the PNR developed in this work where reactants
and products diffuse through the mesoporous silica shell and NIR laser irradiation promotes
the chemical reaction, allowing simultaneous in situ SERS monitoring of the process.
B.V. and M.P.-L acknowledge financial support from Isidro Parga Pondal Program. This
work was funded by the Spanish Ministerio de Econom y Competitividad (CTQ201123167), the European Research Council (CrossSERS, FP7MC-IE 329131, and METACHEM,
grant no. CP-FP 228762-2), Xunta de Galicia (INBIOMED-FEDER “unha maneira de facer
Europa”), and Fundación Ramón Areces.
1 (a) Alvarez-Puebla, R. iz-Marz n, L. M.; García de Abajo, F. J. J. Phys. Chem. Lett. 2010, 1, 2428. (b)
Schuller, J. A.; Barnard, E. S.; Cai, W.; Jun, Y. C.; White, J. S.; Brongersma, M. L. Nat. Mater. 2010, 9, 193.
2 Vázquez-Vázquez, C.; Vaz, B.; Giannini, V.; Pérez-Lorenzo, M.; Álvarez-Puebla, R.A.; Correa-Duarte M. A.
J. Am. Chem. Soc. 2013, 135, 13616−13619.
Bilbao, 4-7 Noviembre 2014
Unraveling how Enzymes Can Use Bulky Residues to Drive Site-Selective
C-H Activation: the Case of Rabbit 15-Lipoxygenase Catalyzing
Arachidonic Acid Oxidation
Patricia Saura,a,b Reynier Suardíaz,a,b Laura Masgrau,b José M. Lluch,a,b and Àngels
González-Lafonta,b,*
a
Departament de Química and Institut de Biotecnología i de Biomedicina (IBB), bUniversitat Autònoma de
Barcelona, 08193 Bellaterra, Barcelona, Spain
[email protected]
The regioselective activation of C-H bonds in complex molecules containing a lot of them is
still an exciting challenge in Chemistry. However, many enzymes catalyze these processes
and much can be learnt from the way they work. In particular, each mammalian lipoxygenase
isoenzyme abstracts a hydrogen atom from essentially a unique carbon position.1 In this work
we present a comprehensive quantum mechanics/molecular mechanics (QM/MM)2 study of
the hydrogen abstraction reaction from arachidonic acid (AA) catalized by rabbit 15lipoxygenase (15-rLO).
Most of the products of this reaction arise from the initial hydrogen abstraction from the
carbon C13 of AA. Nevertheless, we have shown that 15-rLO seems able to catalyze not only
the abstraction of H13, but also of H10. After having studied 20 hydrogen transfers, we have
even concluded that the reaction mechanisms for both abstractions are identical (proton
coupled electron transfer processes), with transition state structures matching their geometries
around the shifting hydrogen. In spite of that similarity, the average potential energy barrier
for the H13 abstractions is 4 kcal/mol higher than for the H10 abstractions, in good agreement
with the experimental C13:C10 ratio of 97:3.3
We have found that a subtle steric hindrance by Leu597 and Ile663 is the main cause for that
difference. Driving the strict regiospecificity exhibited by 15-rLO appears to be the essential
function of the bulky side chains of those conserved residues, this way making possible the
vital physiological role of 15-rLO and, probably, of all the mammalian lipoxygenase
isoenzymes. The understanding of how Nature uses residues with the bulkiest aliphatic side
chains to achieve the selective activation of C-H bonds can stimulate the design of efficient
biocatalysts to that aim.
________________________________________________
1 Ivanov, I.; Heydeck, D.; Hofheinz, K.; Roffeis, J.; O'Donnell, V. B.; Kuhn, H.; Walther, M. Arch. Biochem.
Biophys. 2010, 503, 161.
2 Senn, H. M.; Thiel, W. Angew. Chem.-Int. Edit. 2009, 48, 1198.
3 Borngraber, S.; Browner, M.; Gillmor, S.; Gerth, C.; Anton, M.; Fletterick, R.; Kuhn, H. J. Biol. Chem. 1999,
274, 37345.
Highly Diastereo- and Enantioselective Synthesis of Tertiary Thiols from
5H-Thiazol-4-ones
Saioa Diosdado, Julen Etxabe, Joseba Izquierdo, Aitor Landa, Antonia Mielgo, Iurre Olaizola,
Rosa López and Claudio Palomo
Departamento de Química Orgánica I, Facultad de Químicas, Universidad del País Vasco UPV/ EHU. Manuel
Lardizabal 3, 20018 Donostia - San Sebastián, Spain.
[email protected]
An efficient organocatalytic route to tertiary thiols is reported 1 based on conjugate additions
to nitro olefins of 5H-thiazol-4-ones as new sulfur based carbon pronucleophiles. Key for that
realization is the development of ureidopeptide-based Brønsted bases, a new subclass of
Brønsted base catalysts.
Esquema 1
Success in this transformation is presumably due to the reaction model outlined above. This
model nicely accounts for the best behavior of quinolyl thiazolone substrates for this reaction,
in comparison to that of naphthyl based thiazolones which provided adducts with significantly
lower levels of stereoselectivity, both diastereo- and enantioselectivity.
Acknowledgements: UFI QOSYC 11/22, GV IT-291-07, SAIOTEK 2012, MICINN
CTQ2010-21263-C02
1 Diosdado, S.; Etxabe, J.; Izquierdo, J.; Landa, A.; Mielgo, A.; Olaizola, I.; López, R.; Palomo, C. Angew.
Chem. Int. Ed. 2013, 52, 11846–11851.
Bilbao, 4-7 Noviembre 2014
Co-operativity between Magnesium and Alkali Metals: a Template
Approach to Override Directed ortho-Metallations
Antonio J. Martínez-Martínez, Robert E. Mulvey and Charles T. O’Hara
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, United Kingdom,
G1 1XL
[email protected]
Metallation, the conversion of a C-H bond to a more useful C-Metal bond, is one of the most
important reactions in chemistry worldwide. In particular, Directed ortho-Metallation (DoM)
is one of the most used protocols to ortho-functionalise aromatic systems. In this context,
around 95% pharmaceuticals rely on the use of organolithium reagents to metallate at one
point in their synthesis.1 However, organolithiums have some important drawbacks, for
example they can exhibit poor functional group tolerance, react with solvents and often
require low temperature reaction conditions.
During the last years, the utilisation of alkali metal magnesiates in synthetic protocols has
emerged as a leading alternative to organolithiums reagents in a series of regioselective
deprotonations (Metal-hydrogen exchange) and Metal-halogen exchanges.2
Sodium and potassium magnesiates exhibit unique reactivity and selectively activate C–H
bonds which are generally unreactive towards conventional metallation. We have recently
reported the preparation of large mixed-metal amide-containing macrocyclic complexes
coined as pre-inverse crown complexes3 which regioselectively mono- or di-deprotonate
simple arenes (Scheme 1). This communication details a novel templated protocol to
regioselectively ortho,meta’- and meta,meta’-dimetallate selected aromatic systems while
tolerating a wide range of functional groups without the need for cryo-temperatures. 4
Scheme 1: regioselective 3- and 2-metallation of toluene and naphthalene, respectively.
1 Collum, D.; Acc. Chem. Res. 1993, 26, 227.
2 (a) Mulvey, R. E.; Mongin, F.; Uchiyama, M.; Kondo, Y.; Angew. Chem. Int. Ed. 2007, 46, 3802. (b) Haag
B.; Mosrin M.; Ila H.; Malakhov V.; Knochel P.; Angew. Chem. Int. Ed. 2011, 50, 9794.
3 (a) Martínez-Martínez, A. J.; Armstrong D. R.; Conway, B.; Fleming, B. J.; Klett, J.; Kennedy, A. R.;
Mulvey, R. E.; Robertson, S. D. O’Hara, C. T.; Chem. Sci. 2014, 4, 771. (b) Armstrong, D. R.; Kennedy, A.
R.; Mulvey, R. E.; Rowlings, R.; Angew. Chem. Int. Ed. 1999, 38, 131.
4 Martínez-Martínez, A. J.; Kennedy, A. R.; Mulvey, R. E. O’Hara, C. T.; Unpublished results.
Nucleic Acid-based Engineering of Iron Oxide Nanoparticles for Magnetic
Hyperthermia Applications
Raluca Maria Fratila,a,b Vanessa Herrero García,a Jorge Dias,a María Moros Caballeroa and
Jesús Martínez de la Fuentea,c,d
a
Instituto de Nanociencia de Aragon (INA), Universidad de Zaragoza, C/Mariano Esquillor s/n, 50018
Zaragoza, Spain. bFundación ARAID, C/María de Luna 11, Edificio CEEI Aragón, 50018 Zaragoza, Spain.
c
ICMA-CSIC, C/Pedro Cerbuna 12, 50009 Zaragoza, Spain. dInstitute of Nano Biomedicine and Engineering,
Shanghai Jiao Tong University, Dongchuan Road 800, 200240 Shanghai, People’ s Republic of China.
[email protected]
“Smart” multifunctional nanomaterials combine multiple tasks into a single nanoplatform and
can be used as theranostic nanoprobes for simultaneous diagnostics and therapy.1
Superparamagnetic iron oxide nanoparticles (SPIONs) are particularly interesting for this
purpose, due to their ability to generate heat when exposed to alternating magnetic fields
(magnetic hyperthermia). Hyperthermia using SPIONs is nowadays applied as adjuvant
therapy in the treatment of cancer and is receiving increasing attention for hyperthermiamediated drug delivery. Recently in our group we have designed a “molecular thermometer”
based on SPIONs functionalized with complementary DNA strands of different lengths. 2 The
heat generated by the DNA-SPIONs upon application of the magnetic field promoted the
denaturation of the complementary nucleotides and enabled the accurate mapping of the
temperature profile at different distances from the surface of the nanoparticle.
Here we report the use of DNA and peptide nucleic acids (PNAs) for the engineering of
multifunctional iron oxide nanoparticles for hyperthermia-mediated drug delivery. Firstly,
DNA and PNA (different ratios) were covalently conjugated to the surface of 12 nm SPIONs
coated with an amphiphilic polymer bearing carboxyl groups, using standard peptide
chemistry. An indirect method was used to assess the extent of functionalization, based on the
hybridization with a complementary DNA strand bearing carboxyfluorescein (FAM). The
amount of FAM-DNA released upon dehybridization was quantified by fluorescence
spectroscopy. Our preliminary results indicate that the use of PNA increases the efficiency of
the functionalization when compared to only DNA. We are currently working on the
multifunctionalization of these DNA/PNA-SPIONs with complementary DNA chains bearing
folic acid as tumoral marker and Doxorubicin as chemotherapeutic drug (oligo-zipping
strategy). The release of Doxorubicin will be triggered by magnetic hyperthermia when the
temperature in the vicinity of the nanoparticle will be higher than the melting temperature of
the oligonucleotide (oligo-unzipping).
1 (a) Fratila, R. M.; Mitchell, S. G.; del Pino, P.; Grazu, V.; de la Fuente, J. M. Langmuir 2014, DOI:
10.1021/la5015658. (b) Lee, D.-E.; Koo, H.; Sun, I.-C.; Ryu, J. H.; Kim, K.; Kwon, I. C. Chem. Soc. Rev.
2012, 41, 2656.
2 Dias, J. T.; Moros, M.; del Pino, P.; Rivera, S.; Grazu, V.; de la Fuente, J. M. Angew. Chem. Int. Edit. 2013,
52, 11526.
Bilbao, 4-7 Noviembre 2014
Development of FtsZ Inhibitors as New Antibacterial Agents
Marta Artola,a Henar Vázquez-Villa,a Mar Martín-Fontecha,a Laura Ruiz-Avila,b Albert
Vergoñós,b Laura Araujo-Bazán, Sonia Huecas,b Erney Ramírez-Aportela,b,c Pablo Chacón,c
Annabelle Hoegl,d Stephan A. Sieber,d Jose M. Andreub and María L. López-Rodrígueza
a
Dpto. Química Orgánica I, Facultad de Ciencias Químicas, UCM, Madrid, Spain. bCentro de Investigaciones
Biológicas and cInstituto de Química Física “Rocasolano”, CSIC, Madrid, Spain. dLehrstuhl für Organische
Chemie II, TUM, Munich, Germany.
[email protected]
Spread of antibiotic-resistant strains of pathogenic bacteria has boosted an urgent need for
new antibacterials with novel modes of action. In this sense, FtsZ −a widely conserved
tubulin-like GTPase, which has not been targeted yet by any approved antibiotic− has been
proposed as an attractive target due to its essential role in bacterial cell division.1 From a
structural point of view, two main cavities have been identified for ligand binding: (i) the
GTP-binding pocket and (ii) the long cleft between the nucleotide-binding and the C-terminal
domain, known as the synthetic inhibitor PC190723 binding site (Figure 1).2,3 In the last
decade, compounds that specifically target FtsZ and inhibit its function in bacterial division
have been identified mainly by HTS.4a However, the binding modes of most of them are still
unknown.
Here, we will present our latest results on the discovery of FtsZ inhibitors targeting both
binding sites. For the GTP-binding pocket (i), we identified hit 1 from the screening of our inhouse library, and a hit to lead process led to derivative 40 with improved FtsZ-affinity and
antibacterial activity.4b-c This compound inhibits bacterial cell division by disruption of FtsZ
assembly and FtsZ delocalization (Figure 1A,B). Regarding the PC-binding site (ii),
fluorescent derivatives of inhibitor PC190723 were synthesized. Among them, NBD
derivatives were used as valuable tools to successfully set up a fluorescence-based assay for
the identification of new FtsZ inhibitors (Figure 1C).
(i)
(ii)
New inhibitors for
the GTP binding site
PC190723-based
fluorescent probes
(C)
H2L
Anisotropy (r)
Kd = 2.3 μM
MIC = 60 μM (MRSA)
n=2
n=3
n=4
n=6
Kd = 0.5 μM
MIC = 7 μM (MRSA)
(A)
(B)
Control
40 (5 µM)
Control
40 (2.5 µM)
PC190723 (mM)
Figure 1
Acknowledgments: This work has been supported by grants from the Spanish Ministerio de
Economía y Competitividad (MINECO, SAF2010-22198 and SAF2013-48271) and
Comunidad de Madrid (S2010/BMD-2353). The authors thank MINECO for a predoctoral
FPU grant to M.A.
________________________________________________
1 Adams, D.W. et al. Nat. Rev. Microbiol. 2009, 7, 642-653.
2 Tan, C.M. et al. Sci. Transl. Med. 2012, 4, 126ra35.
3 (a) Haydon, D.J. et al. Science 2008, 321, 1673-1675. (b) Andreu, J.M. et al. J. Biol. Chem. 2010, 285,
14239-14246.
4 (a) Schaffner-Barbero, C. et al. ACS Chem. Biol. 2012, 7, 269-277. (b) Ruiz-Avila L.B. et al. ACS Chem.
Biol. 2013, 8, 2072-2083; (c) Artola, M. et al. ACS Chem. Biol. 2014, under revision.
Hydride Ligands in Orbit around Low-Coordinate Metal Centres
Manuel A. Ortuño,a Pietro Vidossich,a Salvador Conejerob and Agustí Lledósa
a
Departament de Química, Universitat Autònoma de Barcelona, 08193 Cerdanyola del Vallès, Spain.
Departamento de Química Inorgánica, CSIC and Universidad de Sevilla, Instituto de Investigaciones Químicas,
Avda. Américo Vespucio 49, 41092 Sevilla, Spain
[email protected]
Hydrides in transition metal chemistry are highly mobile ligands and can display an extensive
dynamics.1 This contribution presents a new kind of fluxional process which involves a
hydride motion (orbiting) around low-coordinate metal centres (Scheme 1).
Particularly, electron-deficient Pt(II) species can play an important role as intermediates in
relevant reactions, e.g. C–H and H–H bond activations.2 In this regard, a family of lowcoordinate hydride compounds [PtH(NHC)2]+ (NHC = N-heterocyclic carbene) have been
recently characterised.3 Concerning the ligand ItBu (1,3-di-tert-butyl-imidazol-2-ylidene),
NMR experiments show no agostic interactions at the vacant site of [PtH(ItBu)2]+. However,
Density Functional Theory (DFT) calculations claim otherwise, displaying a clear agostic
interaction between Pt and one methyl of the tBu group. According to DFT, this controversy
is explained in terms of a fast orbiting motion of the hydride around Pt, which averages the
NMR signals and precludes the detection of agostic interactions in solution. This type of
fluxional event comes out in other Ir-based systems,4 and appears as an important feature to
take into account for a consistent interpretation of NMR spectra.
Scheme 1: orbit-like motion of hydride ligands
Financial support from Ministerio de Economía y Competitividad (projects CTQ2011-23336 and
CTQ2013-45011) is acknowledged. M.A.O. also thanks the Ministerio de Educación, Cultura y
Deporte for a research grant (FPU).
1 Maseras, F.; Lledós, A.; Clot, E.; Eisenstein, O. Chem. Rev. 2000, 100, 601.
2 Ortuño, M. A.; Conejero, S.; Lledós, A. Beilstein J. Org. Chem. 2013, 9, 1352.
3 Rivada-Wheelaghan, O.; Roselló-Merino, M.; Ortuño, M. A.; Vidossich, P.; Gutiérrez-Puebla, E.; Lledós, A.;
Conejero, S. Inorg. Chem. 2014, 53, 4257.
4 (a) Scott, N. M.; Pons, V.; Stevens, E. D.; Heinekey, D. M.; Nolan, S. P. Angew. Chem. Int. Ed. 2005, 44,
2512. (b) Phillips, N.; Rowles, J.; Kelly, M. J.; Riddlestone, I.; Rees, N. H.; Dervisi, A.; Fallis, I. A.;
Aldridge, S. Organometallics 2012, 31, 8075.
Bilbao, 4-7 Noviembre 2014
New Ruthenium Catalyzed Cyclizations: Dihydrobiphenylenes via [2+2+2]
Cycloadditions of o-Ethynylstyrenes
Carlos González-Rodríguez, Silvia García-Rubín, Jesús A. Varela and Carlos Saá
CIQUS - Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares. C/ Jenaro de la
Fuente s/n , Campus Vida, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain
[email protected]
Benzannulated cyclobut(adi)ene derivatives, e.g. biphenylene, are intrinsically attractive
molecules that might be useful as spacers and building blocks for designing new materials
with advanced electronic properties.1 Very recently, biphenylenic graphene has been proposed
as one of these organic materials due to the smart combination of aromatic and antiaromatic
characters of the six and four-membered rings.2 New efficient synthetic strategies to these
type of materials are highly desirable.
Herein we described a new and efficient synthetic route to dihydrobiphenylenes that involves
a mild Ru(II)-catalyzed [2+2+2] dimerization of ortho-ethynylstyrenes with alkynes.3 We
have also achieved the direct transformation of these dihydrobiphenylenes into asymmetric
halogenated terphenyls under radical halogenation conditions.
Scheme 1
Acknowledgements: This work was supported by MICINN (projects CTQ2011-28258, CTQ201123459, and Consolider Ingenio 2010 (CSD2007-00006)), Xunta de Galicia, the European
Development Fund (projects CN2011/054 and EM 2012/051), the DGA (E35), and the European
Social Found (FSE). C.G.-R. thanks the MICINN for a Juan de la Cierva Contract (JCI-2011-09946).
1 a) Shepherd, M. K. Cyclobutadienes: The Chemistry of Benzocyclobutene, Biphenylene and Related
Compounds; Elsevier: Amsterdam, 1991; b) Sadana, A. K.; Saini, R. K.; Billups, W. E. Chem. Rev. 2003,
103, 1539-1602.;c) Chaumontet, M.; Retailleau, P.; Baudoin, O. J. Org. Chem. 2009, 74, 1774-1776.
2 Schlütter, F.; Nishiuchi, T.; Enkelmann, V.; Müllen, K. Angew. Chem. Int. Ed. 2014, 53, 1538.
3 García-Rubín, S.; González-Rodríguez, C.; García-Yebra, C.; Varela, J. A.; Esteruelas, M. A.; Saa, C.
Angew. Chem. Int. Ed. 2014, 53, 1841-1844.
Ultrafast Photophysics of Pyrrole and 2,5-Dimethylpyrrole
Virginia Ovejas, Marta Fernández-Fernández, Raúl Montero and Asier Longarte.
Departamento de Química Física. Universidad del País Vasco (UPV/EHU). Apart. 644, 48080 Bilbao, Spain
[email protected]
Pyrrole and some simple derivatives are relevant heteroaromatic chromophoric units that
often appear as part of more complex molecular species, in some cases, with relevant
biological significance. Understanding the mechanism involved in the relaxation of the
pyrrolic unit after UV radiation absorption, can notably help to disentangle the photochemical
and photophysical properties of molecular systems containing it. Pyrrole complex dynamics is
known to be driven by the presence of πσ* type states, which result from the promotion of a π
electron into the 3s orbital of Nitrogen, becoming a prototypical system for the study of the
ultrafast processes triggered by this type of excitations.
Our group is engaged in tracking the relaxation dynamics of these aromatic molecules
isolated in the gas phase, by applying pump/probe ionization based techniques with
femtosecond resolution. Herein, we present a study on the ultrafast evolution of pyrrole and
2,5-dimethylpyrrole (DMP) after excitation in the 290-217 nm portion of the UV absorption
spectrum. Both systems exhibit ultrafast dissociation along the N-H stretching coordinate of
the πσ* state, which in the case pyrrole can not be reached by direct excitation from the
ground state. The implications of these findings in the photochemistry of pyrrole
chromophore containing species will be discussed.
Figure 1: a) Typical transient collected of 2.5-dimethylpyrrole with their fit. b) Photoelectron
images recorded at 0fs time delay of 2.5-dimethylpyrrole.
Bilbao, 4-7 Noviembre 2014
Sensory Membranes and Coated Fibers for High Acidity Colorimetric
Sensing
Miriam Trigo-López, Jesús Luis Pablos, Asunción Muñoz, Saturnino Ibeas, Felipe Serna,
Félix Clemente García and José Miguel García
Departamento de Química, Facultad de Ciencias, Universidad de Burgos, Plaza Misael Bañuelos s/n, 09001,
Burgos
[email protected]
The precise control of the acidity or basicity of different media is fundamental for the
chemical, cosmetic and household industry, for environmental control, and also in life
science. Its control is usually carried out in the standard pH scale (1 to 13) in aqueous media,
but there is a significant need to measure the acidity of environmental systems beyond the pH
scale, and non-aqueous environments, such as air. To reach this goal, we describe reusable
colorimetric sensory polymers, which have pendant azo and amino groups both as proton
receptors and chromogenic moieties. In the presence of highly acidic media, aqueous or in air,
a proportional color change occurs for the rapid, precise, and inexpensive measurement of the
acidity even outside of the pH scale.
The polymers incorporate the acid response azo and amino motifs into high-performance
aromatic polyamides1 or polyacrylates with gel behaviour.2 These materials can be prepared
or transformed into highly manageable materials such as films, membranes, or coatings for
commodity cotton fiber of high-tech meta- or para-aromatic polyamide fibers.
Scheme 1: Acid response for a) acrylic polymers and b) polyamides
We gratefully acknowledge the financial support provided by the Spanish Ministerio de
Economía y Competitividad-Feder (MAT2011-22544) and by the Consejería de EducaciónJunta de Castilla y León (BU232U13))
1 Trigo-López, M.; Pablos, J. L.; García, F. C.; Serna, F.; and García, J. M.; J. Polym. Sci., Part A: Polym.
Chem. 2014, 52, 1469–1477
2 Pablos, J.L.; Trigo-López, M.; Serna, F.; García, F. C.; García, J. M.; Chem. Commun., 2014, 50, 2484-2487.
Towards Self-Assembled Tubular Architectures
David González-Rodríguez,* Ana López-Pérez, Nerea Bilbao, Jorge Camacho, Carlos
Montoro, Sonia Romero-Pérez, Violeta Vázquez-González, Maria Teresa Aranda, Raquel
Chamorro, Maria José Mayoral
Nanostructured Molecular Systems and Materials group, Departamento de Química Orgánica, Universidad
Autónoma de Madrid, 28049, Madrid, Spain.
[email protected]
Our project aims at establishing unconventional and versatile strategies towards organic
nanofibers or nanotubes whose size, composition, internal structure, and function can be
rationally predesigned and controlled at the nanoscale. In a first stage, specific cyclic
tetramers are formed from 4 monomeric -conjugated subunits by hydrogen-bonding
interactions between perpendicular directors.1,2 These discrete tetramers then stack into highly
ordered tubular nanostructures guided by the cooperative action of the parallel directors. We
want to focus on two main objectives for the application of such organic nanostructured
materials:
1. The design and preparation of optoelectronic devices, such as plastic solar cells, where
nanostructured fibers are integrated within the active layers. The major goal is to determine
the influence of the molecular organization and the morphology at the nanoscale on the
performance of the device, and to try in this way to set new records in device efficiency;
2. The fabrication of nanoporous materials for the selective separation, storage or catalytic
transformation of (bio)molecules in which the size, the shape ratio, and the internal
functionalization of the nanopores can be custom-tailored.
Cyclic Tetramers
Monomers
Self-assembled
Nanotubes
Scheme 1: self-assembly strategy towards nanostructured tubular architectures
1 a) González-Rodríguez, D.; van Dongen, J. L. J.; Lutz, M.; Spek, A. L.; Schenning, A. P. H. J.; Meijer, E. W.
Nature Chem. 2009, 1, 151.; b) González-Rodríguez, D.; Janssen, P. G. A.; Martín-Rapún, R.; De Cat, I.; De
Feyter, S.; Schenning, A. P. H. J.; Meijer, E. W. J. Am. Chem. Soc. 2010, 132, 4710.
2 a) González-Rodríguez, D.; Schenning, A. P. H. J. Chem. Mater. 2011, 23, 310; b) Schenning, A. P. H. J.;
González-Rodríguez, D. in "On the Role of Hydrogen-Bonding in the Nanoscale Organization of Conjugated Materials", Organic Nanomaterials, Torres, T.; Bottari, G. (Eds.), Wiley, 2013, chapter 2, pp.
33-27.
Bilbao, 4-7 Noviembre 2014
Conformational Flexibility of Seven-membered Rings: the Rotational
Spectrum of Azepane.
M. Vallejo-López,a D. Wachsmuth,b M. K. Jahn,b A. Lesarria, J.-U. Grabow,b
a
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid,
Paseo de Belén, 7, 47011, Valladolid (Spain). bInstitut für Physikalische Chemie und Elektrochemie, Leibniz
Universität Hannover, Callinstrabe 3A, 30167 Hannover (Germany)
[email protected]
The conformational flexibility of seven-membered rings motivates the study of different
molecules of structural or biological interest like azepane. Previous results of our group have
shown different conformational landscapes for substitutions in the heterocyclic rings of
oxacycloheptane1 and caprolactone.2
In this work we present experimental and computational results on azepane. Five most stable
conformers describe the most important features of the PES of the molecule, three of them
within a window energy of 5 kJ mol-1. Ab initio and DFT results will be compared.
The experimental rotational spectrum in the 2-20 GHz were recorded using supersonic jet
Fourier transform microwave spectroscopy, in particular broadband chirped-pulse IMPACTFTMW techniques developed in Hannover. Three different conformers were unambiguously
identified in the spectrum and rotational, centrifugal distortion and nuclear quadrupole
coupling hyperfine parameters were accurately determined.
Scheme 1: the three detected conformers of azepane.
________________________________________________
1 Borter, J.-H.; Wachsmuth, D., Jahn, M. K.; Dewald, D. A.; Grabow, J.-U.; Lesarri, A. National
Bunsentagung conference, 2014,Poster P9-18.
2 Jahn, M. K.; Dewald, D.; Vallejo-López, M.; Cocinero, E. J.; Lesarri, A.; Zou, W.; Cremer, D.; Grabow, J.U. Chem. Eur. J. 2014, 20, DOI:10.1002/chem.01403379.
Towards New Porphyrin-Phthalocyanine Hybrid Derivatives
Alejandro Díaz-Moscoso, Sonia Remiro-Buenamañana and Andrew N. Cammidge
School of Chemistry, University of East Anglia, NR4 7TJ, Norwich (UK)
[email protected], [email protected]
Porphyrins and phthalocyanines are well-known, ubiquitous macrocycles that bring colour to
our lives, but also have been extensively exploited by Nature and humankind to perform
specific electro- and photochemical tasks.1 The development of nanotechnology and
nanochemistry in the near future will surely take advantage of these versatile compounds in
fields like molecular electronics and molecular machines. But the sophisticated and intricate
chemical designs that this fields will require are threatened by structural limitations of current
porphyrin and phthalocyanine derivatives.
In this work, we present our recent achievements in the search, design and development of
porphyrin-phthalocyanine hybrids and their derivatives. These structures are based on
phthalocyanine with one meso-nitrogen substituted by a meso-carbon functionalised with an
aryl moiety. They have the potential of merging the physic-chemical properties of both parent
compounds, allowing new synthetic and functional possibilities. We have recently developed
a new and versatile strategy, based on aryl-aminoisoindolines controlled macrocyclisation,
that gives straightforward access to these derivatives, allowing us to explore unprecedented
synthetic possibilities.2 An overview of the development of the new methodology will be
given together with some remarkable examples.
N
N
N
N
N
R
N
R
M
N
N
Phthalonitrile
Template
20 - 40%

NH2
N
R' N
N B
N
N
New
Derivatives
R
5 - 15%
Scheme 1
Funding from the EU (Marie Curie Actions) and the University of East Anglia (UEA) is
gratefully acknowledged.
1 The Porphyrin Handbook; Vols 1-20 (Kadish, K. M., Smith, K. M., Guilard, R., Eds.); Academic Press:
Boston, MA, 2003.
2 (a) Díaz-Moscoso, A.; Tizzard, G. J.; Coles, S. J.; Cammidge, A. N. Angw. Chem. Int. Ed. 2013, 52, 10784.
(b) Alharbi, N.; Díaz-Moscoso, A.; Tizzard, G. J.; Coles, S. J.; Cook, M. J.; Cammidge, A. N. Tetrahedron,
2014, 70, 7370.
Bilbao, 4-7 Noviembre 2014
Tailoring of a 10-Vertex Rhodathiaborane System for Homogeneous
Catalysis Applications
Susana Luaces, Ramón Macías and Luis A. Oro
Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza-Consejo Superior de
Investigaciones Científicas, 50009-Zaragoza, Spain
[email protected]
One of the main goals in organometallic chemistry is the introduction of ligands capable of
bestowing new reactivity on transition metal centres. Nowadays, the activation of small
molecules, such as H2, CO2 or NH3, and the development of efficient selective homogeneous
catalysts are attracting a high research interest. In this regard, our research group has been
focused on the introduction of heteroboranes as non-innocent-ligands in the coordination
sphere of the transition metal centres, thereby giving to the system new bifunctional acid/base
properties.1,2
Herein, we describe the development of a 10-vertex rhodathiaborane system which shows a
remarkably redox flexibility in the reaction with ethylene and in the activation of hydrogen
(see Scheme below). Thus, this system has been tested in the catalytic hydrogenation of
alkenes and alkynes. Furthermore, trying to explore other catalytic processes, we have
demonstrated that the tailoring of the heteroborane fragment improves the selectivity in the
catalytic hydrosilylation of terminal alkynes towards α-vinylsilanes, a reaction of interest in
organic synthesis.
H
H
H
redox flexibility
H
selective hydrosilylation
H
H
SiR3
Ph3P
H2, PPh3
Ph3P
Ph3P
Rh
PPh3
H
S
H
B
Ph3P
Ph3P
Rh
Rh
S
CH3CH3
PPh3
B
R
H
L
H
S
H
R
B
+
CH3CH3
H PPh3
H
PPh3
hydrogen activation
H2
CH3CH3
Rh
HSiR3
+
2 %, mol
SiR3
R
+
L = PPh3, 2-EtPy, 2-MePy
R
SiR3
PPh3
S
B
83-95 %
Scheme 1: reactions with C2H4 and H2 (left) and hydrosilylation of terminal alkynes (right).
________________________________________________
1 (a) A. Álvarez, R. Macias, J. Bould, M. J. Fabra, F. J. Lahoz, L. A. Oro, J. Am. Chem. Soc., 2008, 130,
11455. (b) Álvarez, R. Macias, M. J. Fabra, F. J. Lahoz, L. A. Oro, J. Am. Chem. Soc., 2008, 130, 2148.
2 (a) B. Calvo, R. Macías, C. Cunchillos, F. J. Lahoz, L. A. Oro, Organometallics, 2011. (b) B. Calvo, R.
Macias, M. J. Artigas, F. J. Lahoz, L. A. Oro, Chem. Eur. J., 2013, 19, 3905.
Synthesis of New Triazolium Cations Following a “Double-Click” Strategy
Zaira Monasterio and Jesús Mª Aizpurua*
Department of Organic Chemistry-I, University of the Basque Country UPV/EHU, Joxé Mari Korta R&D
Center, Avda. Tolosa, 72, Donostia-San Sebastián, Spain
[email protected]
3-N-alkyl-1,2,3-triazolium salts constitute an example of “post-click” chemistry arising from
the “click” pool, with remarkable applications due to their use as functional ionic liquids, as
precursors of mesoionic carbenes,1 or as components of supramolecular assemblies and
molecular machines.2
Herein, we report the synthesis of three novel families of bis-triazolium and mixed triazoliumtriazole compounds 1-3. The preparation strategy involves a combination of alkyne-azide
[3+2] cycloaddition reactions, both Cu(I)-catalysed or metal-free, and site-selective Nalkylation reactions using functionalized alkyl triflates.
Scheme 1: “Double-Click” strategy.
Z. M. thanks University of the Basque Country UPV/EHU (10/2010) for financial support.
1 Aizpurua, J. M.; Sagartzazu-Aizpurua, M.; Monasterio, Z.; Azcune, I.; Mendicute, C.; Miranda, J. I.; GarcíaLecina, E.; Altube, A.; Fratila, R. M. Org. Lett. 2012, 14, 1866.
2 (a) Aizpurua, J. M.; Sagartzazu-Aizpurua, M.; Azcune, I.; Miranda, J. I.; Monasterio, Z.; García-Lecina, E.;
Fratila, R. M. Synthesis 2011, 17, 2737. (b) Aizpurua, J. M.; Fratila, R. M.; Monasterio, Z.; Pérez-Esnaola,
N.; Andreieff, E.; Irastorza, A.; Sagartzazu-Aizpurua, M. New. J. Chem. 2014, 38, 474.
Bilbao, 4-7 Noviembre 2014
Antimicrobial Capsules Assembled from Polyoxometalates and Chitosan
Scott G. Mitchell,* Laura De Matteis* and Jesús M. de la Fuente
Instituto de Nanociencia de Aragón. Universidad de Zaragoza, Campus Rio Ebro, Edif. I+D, 50018-Zaragoza
[email protected]
One of the principle advantages offered by nanohybrid materials is the possibility to construct
modular composite assemblies derived from varied and responsive components.
Polyoxometalates (POMs) are a diverse class of nanoscale molecular metal-oxides
characterised by a broad and versatile range of physicochemical properties. 1 Their redox
behaviour lends them to a wide variety of applications and - due to their high electronic
charge - display a particular affinity towards biomolecules.2 For most bioapplications, the use
of polymeric nanoscaffolds are convenient for a number of factors, including controlled drug
delivery and release as well as improving interactions with cells.3 This presentation reports
the synthesis, characterisation and antibacterial activity of a series of nanometre-sized
capsules obtained through the supramolecular assembling of POMs, the naturally occurring
polymer chitosan and cationic surfactant cetyltrimethylammonium bromide (CTAB). Using a
micelle-based approach, the surfactant is used as a cationic nucleating agent as well as a tool
to trap the POMs before being enveloped by the structure-directing chitosan polymer matrix.
The antibacterial activity of these nanocomposites was evaluated against a non-pathogenic
strain of E.coli.4 Environmental Scanning Transmission Electron Microscopy images of E.coli
incubated with these capsules provide demonstrate how each capsule variant elicits distinct
responses from the bacterium cell, indicative of different particle-bacterium interactions. The
increased antibacterial activity of the nanocapsules (compared with other examples)5 could be
attributed to both their shape and size as well as the nature of the encapsulated POM.
Figure 1
1
2
3
4.
5.
Cronin, L. and Müller, A. Chem. Soc. Rev., 2012, 41, 7333.
Stroobants, K.; Absillis, G.; Moelants, E.; Proost, P.; Parac-Vogt, T. N. Chem. Eur. J., 2014, 20, 3894.
Felice, B.; Prabhakaran, M. P.; Rodríguez, A. P.; Ramakrishna, S. Mat. Sci. Eng. C, 2014, 41, 178.
De Matteis, L.; Mitchell, S. G.; M. De la Fuente, J. J. Mater. Chem. B 2014, DOI: 10.1039/c4tb01460j
Fiorani, G.; Saoncella, O.; Kaner, P.; Altinkaya, A.; Figoli, A.; Bonchio M.; Carro, M. J. Clust. Sci., 2014,
25, 839.
Conjugate Additions and Friedel-Crafts Reactions of p-Quinols:
Stereoselectively access to (Poly)heterocyclic systems.
Carolina García García, M. Carmen Carreño and María Ribagorda
Departamento de Química Orgánica, Universidad Autónoma de Madrid, C/ Francisco Tomás y Valiente 7,
28049, Madrid
[email protected]
p-Quinols are a privilege kind of structures that have been used by organic chemists in the last
decades. We have developed the synthesis of polyheterobicyclic and tricyclic systems by
reaction of p-quinols with aldehydes and imines in a base catalyzed domino process that
embrace a 1,2-addition/oxa (aza)-Michael reaction or a 1,2-addition/aza-Michael/Aza-DielsAlder process (¡Error! No se encuentra el origen de la referencia., left bicyclic and
trycyclic structures).
We have studied the enantioselective intermolecular Friedel-Crafts reaction of different pquinols with indoles in the presence of a catalytic amount of a chiral Phosphoric acid (¡Error!
No se encuentra el origen de la referencia.). Intramolecular Friedel-Crafts reaction of pquinols bearing an indolylalkyl moeity at C-4 position have been also achieved, opening a
new access to different hydro-benzo[c]carbazoles systems (¡Error! No se encuentra el
origen de la referencia.).
Scheme 1
Compuestos Ciclometalados de Ir(III) con Ligandos Alquinilo Puente
Patricia Montaño, Julio Fernández, Nora Giménez, Elena Lalinde, M. Teresa Moreno y Sergio
Sánchez
Bilbao, 4-7 Noviembre 2014
Compuestos Ciclometalados de Ir(III) con Ligandos Alquinilo Puente
Patricia Montaño, Julio Fernández, Nora Giménez, Elena Lalinde, M. Teresa Moreno y Sergio
Sánchez
Departamento de Química – Centro de Investigación en Síntesis Química. Universidad de La Rioja, 26006,
Logroño, España.
[email protected]
La química de los compuestos metálicos con ligandos alquinilo ha sido de gran interés
durante los últimos años, debido a su gran riqueza estructural y las interesantes propiedades
fotofísicas que presentan. Una de las líneas de trabajo de nuestro grupo de investigación se ha
centrado en la síntesis y estudio de las propiedades fotofísicas de alquinil derivados homo y
heteropolinucleares de platino1 incluyendo en ocasiones ligandos cromóforos ciclometalados.2
Por otro lado, frente al creciente interés que han despertado compuestos fosforescentes
ciclometalados de Ir(III), y las interesantes propiedades que se podrían esperar de la
combinación de ligandos alquinilo y ligandos ciclometalados en el centro de iridio resulta
sorprendente que el estudio de este tipo de compuestos esté casi sin explorar. En este
contexto, solo se han descrito recientemente compuestos mononucleares del tipo
[Ir(C^N)(CCR)L].3
Siguiendo con nuestro interés en compuestos cicloplatinados con ligandos alquinilo puente,
hemos diseñado nuevos sistemas homo y heteropolinucleares ciclometalados de Ir(III) con
ligandos alquinilo puente. Así, en esta comunicación se presenta la síntesis de nuevos
compuestos homo dinucleares [Ir(ppy)2(µ-C≡CR)2]2 (R = Tol, C6H4OMe-4, 1-Np, tBu),
estabilizados mediante la formación de un sistema de doble puentes alquinilo :2 y de
clusters tetranucleares heterometálicos [{Ir(ppy)2(C≡CR)2}2M2] (M = Ag, Cu ; R = Tol,
C6H4OMe-3, C6H4CF3-4, tBu) en los que el heterometal M se estabiliza mediante
interacciones de tipo 2-alquinilo e interacciones metal-metal. Se han estudiado en detalle las
propiedades ópticas de estos compuestos para evaluar la influencia del sustituyente del grupo
alquinilo y la naturaleza del heterometal en la luminiscencia.
C Cα
ß
Ir
Ir
Ag
Figure 1
________________________________________________
1 Berenguer, J. R.; Lalinde, E.; Moreno, M. T., Coord. Chem. Rev. 2010, 254 (7-8), 832.
2 Díez, Á.; Lalinde, E.; Moreno, M. T., Coord. Chem. Rev. 2011, 255 (21-22), 2426.
3 (a) Gildea, L. F.; Batsanov, A. S.; Williams, J. A. G., Dalton Trans. 2013, 42 (29), 10388. (b) Kessler, F.;
Curchod, B. F. E.; Tavernelli, I.; Rothlisberger, U.; Scopelliti, R.; Di Censo, D.; Grätzel, M.; Nazeeruddin,
M. K.; Baranoff, E., Angew. Chem. Int. Ed. 2012, 51 (32), 8030; (c) Fu, J. Z.; Zhang, X.; Wang, J. Y.; Zhang,
L. Y.; Chen, Z. N., Inor. Chem. Commun. 2012, 22 (0), 123.
Síntesis de 3,3´-Diheteroarilalcanales Mediante una Reacción One Pot
Dienamina e Ión Iminio Tipo Friedel-Crafts
María Frías, José Alemán*
Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco
[email protected]
Los diheteroarilalcanos son productos naturales
de gran importancia tanto en química como en
biología, principalmente debido a sus
propiedades analgésicas y antitumorales entre
otras.1 Dada su potente actividad biológica
frente a un gran número de dianas
farmacológicas, la comunidad científica ha
centrado su atención en la síntesis asimétrica de
éstos.
Basados en nuestra experiencia en organocatálisis2 y en la química de dienamina,3 nuestra
aproximación sintética consiste en una primera reacción de dienamina para formar el primer
anillo heterocíclico y posteriormente la adición al medio de reacción de otro anillo
heterocíclico para dar lugar a los diheteroarilalcanales enantioméricamente enriquecidos
mediante una reacción de iminio tipo Friedel-Crafts. En esta comunicación presentamos la
optimización de la reacción, su alcance y también algunas derivatizaciones llevadas sobre
estos sustratos.
Esquema 1
1 (a) S. Podder and S. Roy, Tetrahedron, 2007, 63, 9146. (b) S. Podder, J. Choudhury, U. Kanti y S. Roy, J.
Org. Chem., 2007, 72, 3100 y sus referencias citadas;
2 (a) Cecilia Martín-Santos et al, ChemCatChem 2012, 4, 976. (b) Cecilia Martín-Santos et al. Angew. Chem.
Int. Ed. 2014, 53, 8184.
3 C. Mannich, K. Handke, K. Roth, Ber. Dtsch. Chem. Ges. 1936, 69, 2112.
Bilbao, 4-7 Noviembre 2014
The Structural Equivalence between the Methyl Groups in Puckered 3, 3Dimethyl Oxetane
Alberto Macario, Susana Blanco, Juan C. López
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid,
47011 Valladolid, Spain.
[email protected]
The standard concept of molecular structure has to be reconsidered when the molecule
presents large amplitude vibrations. This point of view, based on the assignment of definite
bond lengths and angles, does not always reproduce the experimental spectroscopic data in
those molecules, so that it became necessary to have the information on the large amplitude
molecular vibration potential energy function and the corresponding dynamical path. 3,3dimethyloxetane [1-3](DMO) has a non-planar ring equilibrium configuration (γ = 17.5º) and
a double minimum potential function for ring-puckering with a barrier of 47 cm-1.1,2 The
observation of the endocyclic 13C and 18O monosubstituted isotopologues3 allow to conclude
that the ring is puckered. For the axial and equatorial 13C-methyl groups, it could be then
expected the detection of two different spectra. However, only one species was found.
Therefore, this means that both methyl groups are equivalent, as if the ring would present a
planar structure. In this work we show how consideration of the potential function and a
reasonable path for ring puckering motion to calculate the proper kinetic energy terms, allow
to reproduce the experimental results, not expected from non-dynamical considerations of the
molecular structure.
Figure 1
________________________________________________
1 J. A. Duckett, T. L. Smithson, and H. Wieser, J. Mol Spectrosc. 1978, 69, 159; J. A. Duckett, T L. Smithson
and H. Wieser, J. Mol. Struc. 1979, 56, 157.
2 J. C. López, A. G. Lesarri, R. M. Villamañán and J. L. Alonso, J. Mol. Spectrosc. 1990, 141, 231.
3 R. Sanchez, S. Blanco, A. Lesarri, J. C. Lopez and J. L. Alonso, Phys. Chem. Chem. Phys., 2005, 7, 1157.
Síntesis de Compuestos con Actividad Fotoprotectora
Raúl Losantos and Diego Sampedro
Departamento de Química, Centro de Investigación en Síntesis Química (CISQ), Universidad de La Rioja C/
Madre de Dios 51, 26006 Logroño, La Rioja, Spain.
[email protected]
Parte de la radiación que nos llega del sol es dañina para los organismos vivos, por ello aparte
de los mecanismos que posee la tierra para eliminarla, los organismos han ido perfeccionando
sus sistemas de fotoprotección a lo largo de millones de años. En la actualidad se conocen
varios tipos de metabolitos que presentan este rol biológico, como son las melaninas, la
escitonemina,1 los carotenos y las micosporinas.
Un caso singular son las micosporinas también conocidas como aminoácidos de tipo
micosporina o MAAs. Estos metabolitos presentan unas propiedades físico-químicas2 que
unidas a sus propiedades fotoquímicas justifican su alta eficiencia como fotoprotectores.3
Estos compuestos se dividen en dos grandes grupos atendiendo a su estructura, las
aminociclohexenonas y las aminociclohexeniminas, que presentan una fotoquímica que las
hace candidatas a ser un excelente fotoprotector.
Esquema 1: estructura genérica de aminociclohexenona
y aminociclohexenimina presente en los MAAs.
En esta comunicación se presenta parcialmente la primera síntesis de análogos de los MAAs
con estructura de aminociclohexenimina y las propiedades fotofísicas y fotoquímicas más
relevantes de los análogos sintetizados.
1 F. Garcia-Pichel, R. W. Castenholz, J. Phycol. 1991, 27, 395-409.
2 J. Favre-Bonvin, N. Arpin, C. Brevard, Can. J. Chem. 1976, 54, 1105.
3 D. Sampedro, Phys. Chem. Chem. Phys. 2011, 13, 5584-5586.
Bilbao, 4-7 Noviembre 2014
Nuevos Derivados de 1,10-Fenantrolina Dicuaternizada: Síntesis y Estudios
de Interacción
Sara Sierra, Katerina Duskova, María-José Fernández, María-Selma Arias, Antonio Lorente y
Lourdes Gude
Departamento de Química Orgánica y Química Inorgánica, Universidad de Alcalá, Facultad de Farmacia,
Ctra. Madrid-Barcelona km 33.6,
28871-Alcalá de Henares (Madrid).
[email protected]
Las estructuras de ADN cuádruple son consideradas en la actualidad importantes dianas
terapéuticas, con aplicaciones en oncología. De hecho, dada su abundancia en las regiones
teloméricas y en los promotores de ciertos oncogenes, las moléculas capaces de estabilizar
este tipo de estructuras secundarias del ADN representan una interesante clase de agentes
anti-cancerosos.
Los ligandos selectivos de estructuras cuádruples pueden presentar una gran variedad
estructural. En numerosas ocasiones, son moléculas cargadas positivamente que cuentan con
una extensa superficie aromática. En el caso de un sistema relativamente sencillo como la
1,10-fenantrolina, se han descrito ejemplos de compuestos disustituidos en las posiciones 4,7o 2,9- que pueden interaccionar con el ADN cuádruple con gran afinidad y buena
selectividad. 1,2
En esta comunicación se describe la preparación de una nueva serie de derivados de 1,10fenantrolina dicuaternizada, en la que se han funcionalizado las posiciones 4- y 7- con
cadenas alquílicas conteniendo diversos restos heterocíclicos o aromáticos. Además, se ha
estudiado la estabilización del ADN cuádruple frente a la desnaturalización producida por
estos ligandos mediante la técnica FRET,3 así como evaluado su afinidad y selectividad
mediante diálisis de equilibrio competitiva.
Figure 1
________________________________________________
1 Nielsen, M.C.; Borch, J.; Ulven, T., Bioorg. Med. Chem., 2009, 17, 8241-8246.
2 Wang, L.; Wu, Y.; Chen, T.; Wei, C., Int. J. Biol. Macromol., 2013, 52, 1-8.
3 De Cian, A.; DeLemos, E.; Mergny, J.L.; Teulade-Fichou, M.P.; Monchaud, D. J. Am. Chem. Soc., 2007,
129, 1856-1857.
Unravelling the Mechanism of Water Oxidation Catalysed by Novel tacnbased Ruthenium Complexes
Carla Casadevall, Miquel Costas and Julio LLoret-Fillol
Chemistry Department, University of Girona, Campus Montilivi, 17071 Girona, Spain.
[email protected]
Mechanistic understanding of the metal-catalysed water-oxidation (WO) on a
molecular scale is essential for its development. Since water is abundant and its
oxidation produces O2 as by-product, light-driven WO is the most attractive source of
electrons to be used in a multi-ton scale. However, WO has been identified as the
bottleneck, because it requires a rapid stepwise building up of very high redox
potentials only bearable by few chemical species and, thus, difficult to control against
side oxidative damage. Despite of all these chemical challenges, WO is absolutely
required because it is a fundamental transformation for the development of artificial
photosynthetic systems.
Furthermore, ligands based on 1,4,7-tryazacyclononane (tacn) are very robust and they
have been proved to stabilise metals in high oxidation states1. Therefore, such ligands
constitute an excellent platform for the development and study of oxidation catalysts
based on either first or second row transition metals.
Herein, a novel family of RuII complexes based on the triazacyclononane moiety has
been synthesised and fully characterized. More concretely, the catalytic activity of novel
tetradentate [RuIICl(dmso)(PyMe2tacn)]Cl and pentadentate [RuIICl(Py2Metacn)]Cl
complexes has been studied as water oxidation catalysts. In addition, the WO mechanism
has been elucidated in the basis of different studies such as kinetics, isotopic labelling,
trapping of the intermediates and computational studies.2
Scheme 1: new ruthenium complexes for the mechanistic investigation of WO to O2
________________________________________________
1. (a) Garcia-Bosch, I.; Codolà, Z.; Prat, I.; Ribas, X.; Lloret-Fillol, J.; Costas, M., Chem. Eur. J. 2012, 18 (42),
13269-13273. (b) Prat, I.; Mathieson, J. S.; Güell, M.; Ribas, X.; Luis, J. M.; Cronin, L.; Costas, M., Nat.
Chem. 2011, 3 (10), 788-793. (c) Anna Company; Irene Prat; Jonathan R. Frisch; Ruben Mas-Ballest; Mireia
Güell; Gergely Juhász; Xavi Ribas; Eckard Münck; Josep M. Luis; Lawrence Que, J.; Costas, M., Chem.
Eur. J. 2011, 17, 1622-1634. (d) A. L. Gott, P. C. M., T.J. Podesta, C.W. Tate, Inorg. Chim. Acta 2004, 357,
689-698. (e) W.P. Yip, C. M. H., N.Zhu, T.C. Lau, C.M. Che, Chem. Asian J. 2008, 3, 70-77. (f) C.M. Che,
W. P. Y., W.Y. Yu, Chem. Asian J 2006, 1, 453-458.
2. (a) Fillol, J. L.; Codolà, Z.; Garcia-Bosch, I.; Gómez, L.; Pla, J. J.; Costas, M., Nat Chem 2011, 3 (10), 807813. (b) Zoel Codolà, J. M. C., Beatriz Royo, Miquel Costas, Julio Lloret‐Fillol, Chem. Eur. J. 2013, 19 (22),
7203-7213.
Bilbao, 4-7 Noviembre 2014
Escuaramidas: una Nueva Pieza en el Puzzle de la Organocatálisis
Juan V. Alegre-Requena, Eugenia Marqués-López* y Raquel P. Herrera*
Dpto. de Química Orgánica. Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad
de Zaragoza. E-50009 Zaragoza, tfno.: +34 976761190
[email protected]
Las escuaramidas son compuestos que han irrumpido fuertemente en el mundo de la
organocatálisis desde el primer ejemplo llevado a cabo por Rawal y col. en 2008. 1 Estos
compuestos se han usado satisfactoriamente en otras áreas de la química, pero sin duda, en
ningún campo han tenido el mismo impacto que en la organocatálisis.2 Esto es debido, en
gran parte, a la interesante combinación de usar catálisis promovida por enlaces de hidrógeno
y estructuras quirales bifuncionales.
En nuestro grupo de investigación hemos obtenido recientemente resultados prometedores en
lo que se refiere al uso de este tipo de compuestos como organocatalizadores. Se trata de la
adición de dialquil- o diaril- fosfitos a compuestos carbonílicos (reacción de Pudovik), que
permite la obtención de α-hidroxifosfonatos enantioméricamente enriquecidos, con potencial
actividad biológica (Esquema 1).3 Este resultado es muy interesante ya que los antecedentes
de dicha reacción eran muy escasos. En concreto, sólo había dos ejemplos organocatalíticos
asimétricos previos,4 lo que demuestra la complejidad del proceso.
En esta comunicación se presentan los resultados más recientes en lo que se refiere a dicha
metodología, así como los valores preliminares obtenidos en otros procesos organocatalíticos.
Asimismo, se muestran otros aspectos de interés de las escuaramidas, como por ejemplo estudios
realizados de algunas de sus propiedades.
Esquema 1: hidrofosfonilación asimétrica de aldehídos usando una escuaramida quiral
1 Malerich, J. P.; Hagihara, K.; Rawal, V. H. J. Am. Chem. Soc. 2008, 130, 14416.
2 (a) Storer, R. I.; Aciro, C.; Jones, L. H. Chem. Soc. Rev. 2011, 40, 2330. (b) Alemán, J.; Parra, A.; Jiang, H.;
Jørgensen, K. A. Chem. Eur. J. 2011, 17, 6890. (c) Alegre-Requena, J. V. Synlett 2014, 25, 298.
3 Alegre-Requena, J. V.; Marqués-López, E.; Sanz Miguel, P. J.; Herrera, R. P. Org. Biomol. Chem. 2014, 12,
1258.
4 (a) Wynberg, H.; Smaardijk, A. A. Tetrahedron Lett. 1983, 24, 5899. (b) Uraguchi, D.; Ito, T.; Ooi, T. J. Am.
Chem. Soc. 2009, 131, 3836.
Espectroscopía IRMPD de los Complejos de Inclusión de Cationes Sencillos
en Heptakis-Ciclodextrinas.
Curro Rodrigo-García
Departmento de Sistemas Físicos, Químicos y Naturales, Universidad Pablo de Olavide, Crta Utrera km 1
Sevilla
[email protected]
Este trabajo resulta de la combinación de procedimientos experimentales y teóricos, con la
cooperación de instalaciones y personal de dos centros de países diferentes, con el fin de
determinar la estructura de la asociación del oligosacárido cíclico heptakis-ciclodextrina con
cationes sencillos en vacío.
Por un lado, las medidas experimentales de los espectros de disociación infrarroja por
múltiples fotones (IRMPD) llevados a cabo con el láser de electrones libres (FELIX) en la
Radboud Universiteit de Nijmegen (Países Bajos) nos permiten caracterizar las vibraciones
implicadas en la inclusión de metales alcalinos y aminas pequeñas en el ciclo. Estos espectros
son interpretados mediante la simulación cuántica de diferentes configuraciones estables en la
Universidad Pablo de Olavide, con las que hacemos corresponder los resultados
experimentales, conectando la realidad microscópica con los efectos macroscópicos.
Reconocimientos al equipo de FT-ICR de la instalación FELIX en la Radboud Universiteit de
Nijmegen (Países Bajos) y al departamento de Sistemas Físicos, Químicos y Naturales de la
Universidad Pablo de Olavide de Sevilla (España).
Bilbao, 4-7 Noviembre 2014
Complejos de Iridio con la Diolefina 2,5-Norbornadieno (NBD)
M. Pilar Betoré, Miguel A. Casado, María P. García-Orduña, Fernando J. Lahoz, Víctor Polo,
Luis A. Oro
Departamento de Química Inorgánica, ISQCH, Universidad de Zaragoza-CSIC, 50009 Zaragoza
[email protected]
El fácil acceso sintético a complejos dinucleares de rodio e iridio del tipo [{Ir(µCl)(diolefina)}2] (diolefina = 1,5-ciclooctadieno (COD), tetrafluorobenzobarreleno (TFB)) ha
permitido el desarrollo de una química organometálica muy extensa.1 En este contexto las
diferencias estructurales, de origen tanto estérico como electrónico, entre estas dos diolefinas
inducen una reactividad diferente a los complejos correspondientes. Otra diolefina disponible
comercialmente íntimamente relacionada es 2,5-norbornadieno (NBD), que posee un ángulo
de mordedura más pequeño. Aunque la química de rodio con este dieno es conocida, en el
caso de iridio esta química está mucho menos desarrollada.
En este trabajo de investigación se explora el comportamiento químico de complejos de iridio
con la diolefina NBD. La reacción de sustitución del dieno COD por el dieno NBD en el
complejo dinuclear [{Ir(µ-Cl)(COD)}2] da lugar a un complejo dinuclear de fórmula [{Ir(µCl)(C7H8)3}2],2 en el que formalmente hay tres diolefinas por átomo de iridio. Mediante
difracción de rayos X se puede comprobar como dos de estas unidades de NBD han
experimentado un acoplamiento carbono–carbono inducido por el metal formando un
metalaciclo de cinco miembros, mientras que una de las diolefinas está coordinada en su
modo natural 4-C=C (ver Fig. 1). Este complejo es insoluble; sin embargo su interacción con
ligandos N-, P- y C- dadores da lugar a la formación de aductos mononucleares solubles que
se han caracterizado mediante técnicas de RMN y de rayos X. En algunos casos, dependiendo
de la naturaleza del ligando, se observan fenómenos de inserción del metalaciclo en enlaces
Ir–CO e incluso el acoplamiento C–C de una tercera molécula de NBD formando un
metalaciclo de 7 miembros.
Figura 1: Estructura molecular del complejo [{Ir(µ-Cl)(C7H8)3}2].
Agradecimientos: Proyecto CTQ2012-35665 y Programa CONSOLIDER INGENIO- 2010.
________________________________________________
1 (a) M. A. Esteruelas, L. A. Oro, Coord. Chem. Rev. 1999, 193–195, 557. (b) R. S. Dickson, Organometallic
Chemistry of Rhodium and Iridium, Academic Press, London, 1983.
2 S. A. Bezman, P. H. Bird, A. R. Fraser, J. A. Osborn, Inorg. Chem. 1980, 19, 3755–3763.
Bilbao, 4-7 Noviembre 2014
Chemoselective Hydrogenation of Nitroarenes Using well-defined Mo3S4
Cluster Catalysts
Elena Pedrajas, IvánSorribes, Artem Gushchin, Kathrin Junge, Matthias Beller and Rosa
Llusar
Dpto. de Química Física y Analítica, Universitat Jaume I, AvVicentSosBaynat s/n, 12071, Catellón. Tfno: +34
964 72 80 74
[email protected]
Aromatic amines are widely used as versatile building blocks in the preparation of dyes,
pigments, agrochemicals and polymers. The direct hydrogenation of nitroarenes is the most
environmentally benign and cost-effective methodology for their preparation. Obviously, the
use of heterogeneous catalysts on the bulk industrial scale is preferred.1 However, for the
production of specialties and synthetic applications, where a high control of the
chemoselectivity is required, the vast majority of heterogeneous catalysts still present some
limitations. In this respect, homogeneous catalyst systems through the use of coordination
chemistry lead to a significant improvement on the control of the selectivity for nitroarenes
reduction. Recently, we have reported the transfer hydrogenation of nitroarenes mediated by a
Mo3S4 cluster functionalized with outer diphosphane ligands.2 Here, a fine tuning of the
structure by combining the Mo3S4 cluster unit with diamine or diimine ligands is presented.
These well-defined molecular clusters present a high chemoselectivity in the hydrogenation of
a wide range of nitroarenes bearing other sensitive reducible moieties.
Scheme 1: hydrogenation of nitroarenes catalyzed by Mo3S4 clusters.
1 (a) Jagadeesh, R. V.; Surkus, A-E.; Junge, H.; Pohl, M-M.; Radnik, J.; Rabeah, J.; Huan, H.; Schünemann,
V.; Brückner, A.; Beller, M. Science 2013, 342, 1073. (b) Westerhaus, F.A.; Jagadeesh, R. V.; Wienhöfer,
G.; Pohl, M-M.; Radnik, J.; Surkus, A-E.; Rabeah, J.; Junge, K.; Junge, H.; Nielsen, M.; Brückner, A.;
Beller, M. Nat. Chem. 2013, 5, 537. (c) Corma, A.; Serna, P.;Science 2006, 313, 332.
2 Sorribes, I.; Wienhöfer, G.; Vicent, C.; Junge, K.; Llusar, R.; Beller, M. Angew. Chem. Int. Ed. 2012, 51,
7794.
Cyclopenta[hi]aceanthrylene-based Derivatives as Carbon Nanotubes
Dispersing Agents and Self-assembled, Electron-donor Systems
Virtudes Pardo-Rodríguez,a Giovanni Bottari,a,b Beatriz Ballesterosa and Tomás Torresa,b
a
Departamento de Química Orgánica, Universidad Autónoma de Madrid, 28049-Madrid, Spain.
b
IMDEA-Nanociencia, c/Faraday 9, Campus de Cantoblanco, 28049-Madrid, Spain
[email protected]
Cyclopenta[hi]aceanthrylene (CPA) is a planar, aromatic compound that belongs to the family
of cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs) and that can be formally
considered as a fragment of the oval-shaped C70 fullerene (Figure 1a). Moreover, this carbonrich species has excellent electron affinity (it could be reversibly reduced twice at low
potentials as a result of the 4n+2 stabilization of the dianionic species) which has prompted
the utilization of CPA derivatives as electron acceptor in donor/acceptor blends with poly(3hexylthiophene) (P3HT)1 and in all-carbon D-A copolymers.2 In this work, we have exploited
both the structural and electronic features of CPA for two purposes.
On one hand, CPA derivatives bearing two pendant pyrene (Pyr) moieties have been prepared
and studied as dispersing agents for single-walled carbon nanotubes (SWCNTs)3 taking
advantage of - interactions between the graphene-like SWCNT surface and the planar,
aromatic surface of the CPA-pyrene conjugates (Figure 1b).
On the other hand, CPA derivatives bearing terminal moieties able to form hydrogen-bonding
networks have been synthesized and their self-organization properties in solution investigated
with the aim of obtaining self-organized, electron-donor ensembles (Figure 1c).
a)
b)
SWCNTs
bundles
Pyr
c)
CPA
CPA
CPA
Pyr
Figure 1
1. Wood, J. D.; Jellison, J. L.; Finke, A. D.; Wang, L.; Plunkett, K. N. J. Am. Chem. Soc. 2012, 134, 15783.
2. Jellison, J. L.; Lee, C.-H.; Zhu, X.; Wood, J. D.; Plunkett, K. N. Angew. Chem. Int. Ed. 2012, 51, 12321.
3. Tasis, D.; Tagmatarchis, N.; Bianco, A.; Prato, M. Chem. Rev. 2006, 106, 1105.
Bilbao, 4-7 Noviembre 2014
Aminoalcoholes para la Descomposición de Pesticidas Organofosforados
Daniel Ferri, Andrea Barba-Bon, Ana M. Costero,* Pablo Gaviña y Salvador Gil.
Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad Mixta Universitat Politècnica de
València - Universitat de València y Departamento de Química Orgánica, Universitat de València, Dr Moliner,
50, 46100 Burjassot, Valencia, España.
[email protected]
Los plaguicidas organofosforados (organophosphorus pesticides, OPs), constituyen hoy en día
la clase de plaguicidas más ampliamente utilizada. Se emplean en la agricultura, para proteger
las plantas de enfermedades y de los insectos, en los huertos familiares y también en
veterinaria. Los OPs son considerados más seguros que sus antecesores, los pesticidas
organoclorados, debido a su degradación más rápida a través de procesos microbianos o
ambientales.1 En los últimos años varias agencias gubernamentales, como la EPA, han
reconsiderado el uso de estos plaguicidas debido a sus efectos perjudícales sobre el sistema
nervioso central en los seres humanos.2 En nuestro grupo de investigación se ha estudiado la
detección y discriminación de diversos OPs,3 y también se han realizado estudios de
remediación con compuestos supramoleculares para distintos derivados organofosforados
usados como agentes nerviosos.4 En el presente trabajo se discute la descomposición de
algunos de estos plaguicidas (Azinphos-methyl, Methidathion y Malathion, Figura 1),
utilizando aminoalcoholes como agentes de remediación. Los productos de descomposición
de los OPs se estudian utilizando métodos espectroscópicos, como la resonancia magnética
nuclear (31P, 1H y 13C), la absorción UV-vis y la emisión de fluorescencia.
Figura 1. Estructura de los plaguicidas estudiados.
1 C. Aprea, C. Colosio, T. Mammone, C. Minoia, M. Maroni, Chromatogr. B Analyt. Technol. Biomed. Life
Sci., 2002, 769, 191–219.
2 P.I. Beamer, R.A. Canales, A.C. Ferguson, J.O. Leckie, A. Bradman, Int. J. Environ. Res. Publ. Health,
2012, 9, 73-96.
3 D. Ferri, P. Gaviña, A. M. Costero, M. Parra, J. L. Vivancos, R. Martínez-Máñez., Sensors and Actuators B,
2014, 202, 727–731.
4 A. Barba-Bon, A. M. Costero, M. Parra, S. Gil, R. Martínez-Mañez, F. Sancenón, P. A. Gale, J. R. Hiscock.,
Chem. Eur. J. 2013. 19, 1586–1590.
Chemical Imaging for Detecting Explosives in Human Handprints
Mª Ángeles Fernández de la Ossa, José Manuel Amigo and Carmen García-Ruiz
Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering and University Institute of
Research in Police Sciences (IUICP), University of Alcalá, Ctra. Madrid-Barcelona km 33.600, 28871 Alcalá de
Henares (Madrid), Spain. Department of Food Sciences, Faculty of Life Sciences, University of Copenhagen,
Rolighedsvej 30, DK-1958 Frederiksberg C, Denmark.
[email protected]
Developments in explosive identification are constantly being presented. Unfortunately, the
continuous threat of worldwide terrorist activities are becoming necessary to design new
analytical methodologies for fast and robust explosive detection and identification methods.
In fact, the identification of explosives in a crime scene is still nowadays a challenge.
Specifically, when that identification must be carried out directly from human handprint
residues. Conventional IR spectroscopy, and more specifically near infrared spectroscopy
(NIR) offers the advantages of a fast, robust and non-destructive technique but is limited to
the analysis of very small area of sample during each single measurement. Therefore, a
plausible solution to analyze larger surfaces is the use of NIR hyperspectral imaging (HSI).
HSI combines the non-contact, non-destructive properties of NIR analysis with the
conventional chemical imaging techniques to generate a three-dimensional image (known as
spectral hypercube) containing spatial and spectral information of the sample.
In this work, NIR-HSI, combined with partial least squares discriminant analysis (PLS-DA) is
first used to provide a fast, non-contact, non-invasive and non-destructive method for the
analysis of different explosive residues on human handprints. Volunteers manipulated
individually ammonium nitrate, black powder, single- and double-base smokeless
gunpowders and dynamite samples and after deposited their handprints on plastic sheets.
Polyvinyl sheets containing explosive residues were then analyzed with the NIR-HSI system.
PLS-DA models were built to detect and classify the pixels contaminated with the dynamite
residues. High levels of sensitivity of specificity for all classes defined were obtained,
determining whether a person has been manipulating explosives by the direct analysis of
his/her handprints. We have demonstrated that HSI-NIR combined with chemometrics is a
promising forensic tool for the detection of explosives residues contained in human
handprints avoiding also the influence of sweat or dirtiness commonly present on hands.1
Figure 1: NIR false colour hyperspectral image of a handprints showing the presence of
ammonium nitrate residues as highlighted pixels in pink colour. Spectrum observed of a
specific point identified as explosive residue.
1 (a) Fernández de la Ossa, M.Á.; García-Ruiz, C.; Amigo, J.M. Talanta 2014, 130, 315. (b) Fernández de la
Ossa, M.Á.; Amigo, J.M.; García-Ruiz, C. Forensic Sci. Int. 2014, 242, 228. (c) Fernández de la Ossa, M.Á.;
García-Ruiz, C.; Amigo, J.M. NIR News 2014, 25, 6.
Bilbao, 4-7 Noviembre 2014
Ti-Catalyzed Synthesis of Exocyclic Allenes on Oxygenated Heterocycles
Natalia M. Padial,b Carmen Hernández-Cervantes,a Juan Muñoz-Bascón,b Esther RoldánMolina,b Ignacio Rodríguez-Garcíaa and J. Enrique Oltrab
a
Organic Chemistry, ceiA3, University of Almería, Almería, E-04120, Spain. bDepartment of Organic Chemistry,
Faculty of Sciences , University of Granada, Campus Fuentenueva s/n, E-18071 Granada, Spain.
[email protected]
Along many years, allenes were considered highly unstable compounds or simple chemical
curiosities. In our days, however, a lot of natural products containing the allene motif are
known and, in many cases, they have the allene function in exocyclic disposition.
Furthermore, allenes have proved themselves to be useful building blocks in organic
synthesis. Owing to the growing interest of allenes in pharmacy and contemporary chemistry,
several procedures for allene synthesis have been developed in recent years. In this context,
we recently reported the Barbier-type cyclization of propargyl halides catalyzed by [Cp2TiCl]
(Nugent’s reagent). This novel C-C bond forming reaction directly gave five-, six- and sevenmembered carbocycles and nitrogen-containing heterocycles bearing an exocyclic allene
group.1 Now, we have extended this method to the straightforward synthesis of oxygencontaining heterocycles bearing an exocyclic allene motif.
Scheme 1
Titanium is a relatively inexpensive and abundant metal on Earth and many titanium
derivatives are healthy and eco-friendly. Moreover, based on our previous observations, we
deemed that the Ti-catalyzed synthesis of oxygenated heterocycles bearing an exocyclic
allene could be easily achieved by using the titanocene-regenerating agent, developed in our
laboratory, to close the catalytic cycle.
Acknowledgments: To the Spanish Ministerio de Economía y Competitividad (CTQ201124443) and Junta de Andalucía (P10- FQM-6050).
1 J. Muñoz-Bascón, C. Hernández-Cervantes, N. M. Padial, M. Álvarez-Corral, A. Rosales, I. RodríguezGarcía, J. E. Oltra, Chem., Eur. J. 2014, 20, 801-810
Synthesis and Resolution of the Racemic Mixture of a Receptor Based on a
Benzofuran Scaffold
Omayra H. Rubio, Ángel L. Fuentes de Arriba, Laura M. Monleón, Ángel Gómez Herrero,
Francisco Gómez Herrero, Luis Simón and Joaquín R. Morán
Organic Chemistry Department, University of Salamanca, Plaza de los Caídos 1-5 37008, Salamanca, Spain
[email protected]
Molecular recognition plays an important role in biological systems, such as vancomycin, the
most important antibiotic in the treatment of Staphylococcus aureus. Vancomycin binds to the
dipeptide D-alanyl-D-alanine terminus, thereby inhibiting bacterial cell wall synthesis.
Ogston's work1 was an important contribution to the stereochemical field as it explained
biological enantiospecificity by the three points binding model, which shows that for a chiral
receptor being able to discriminate between two enantiomers, at least three points of the
receptor must interact with three complementary points of the compound which will be
hosted.
In this communication, this methodological approach has been applied to prepare a host based
on a benzofurane scaffold2 whose racemic mixture could be resolved by enantioselective
liquid-liquid extraction with chiral aminoalcohols such as ephedrine or fractional
crystallization with cinchonine.
Once resolved the host, we carried out competitive titrations with different amines (primary,
secondary and tertiary) by enantioselective extractions, which allowed us to calculate the
relative association constant between the two amine enantiomers. We also have extracted
enantioselectively amino acids derivatives like L-alanine cyclohexylthiourea or dinitrobenzoyl
phenylglycine.
Scheme 1: benzofurane derivative receptor and its X-ray structure.
1 Ogston, A.G. Nature 1948, 162, 963.
2 Li, Q.-B.; Zhou, F.-T.; Liu, Z.-G.; Li, X.-F.; Zhu, W.-D.; Xie, J.-W. J. Org. Chem. 2011, 76, 7222-7228.
Bilbao, 4-7 Noviembre 2014
Femtosecond Transient Absorption Spectroscopy Of Simple
Heteroaromatic Chromophores
Marta Fernández-Fernández, Virginia Ovejas , Raúl Montero and Asier Longarte
Departamento de Química Física. Universidad del País Vasco (UPV/EHU). Apart. 644, 48080 Bilbao, Spain
[email protected]
Aromatic chromophores may be considered as molecular subunits that are characterized by
having strong ππ* transitions, providing the molecular systems with the ability to efficiently
absorb UV-Vis radiation. Additionally, mixed with the ππ* states, these molecules may appear
πσ*, which resulting from the promotion of a π electron from the aromatic moiety into the 3s
orbital of a heteroatom X (usually O or N), acquire dissociative character along the X-H stretching
coordinate. As a consequence, the preparation of the molecule into these πσ* states gives rise
to a complicated photophysics and photochemistry in the condensed phase, which are
responsible for such important processes as the proton concerted electron transfer (PCET)
,photoacidity, etc.
The modern time-resolved techniques based in ultrashort laser pulses appear as very versatile
tools to unravel the dynamics of these processes, allowing us to track the evolution of the
molecule in real time, from the early instants after the preparation of the excited specie, to the
formation of photoproducts. In this work we present the design and construction of a transient
absorption set-up for the study of the ultrafast electronic relaxation of aromatic
chromophores. The instrument incorporates the last available developments of the technique
and permits the excitation of the sample in an interval ranging from the visible, to the far UV
at 200 nm, while the response may be probed by white light continuum extending from 330 to
1050 nm. Time resolved measurements are perfomed with a resolution of 50 fs.
The recently built apparatus is being used to study the role of the πσ* states in the
photochemistry of the aniline molecule in aqueous media. Herein, preliminary transients after
excitation at 267 nm, the energy region where the πσ* is found mixed with more bright ππ*
transitions, will be shown. The data reveal the formation of the radical cation and the solvated
electron in ultrafast time scales. The implications of these observations will be discussed.
700fs
750fs
800fs
850fs
900fs
950fs
1000fs
1050fs
350
400
450
500
550
600
Wavelenght (nm)
Figure1. Time evolution of aniline absorption spectrum, excited at 267 nm.
Síntesis de Policiclos mediante Hidroarilación de Alenos Catalizada por
Oro
Sara Cembellín,a Benito Alcaide,a Pedro Almendrosb y Teresa Martínez del Campoa
a
Grupo de Lactamas y Heterociclos Bioactivos, Departamento de Química Orgánica, Unidad Asociada al CSIC,
Facultad de Química, Universidad Complutense de Madrid, 28040-Madrid. bInstituto de Química Orgánica
General, IQOG, CSIC, Juan de la Cierva 3, 28006-Madrid.
[email protected]
La química de alenos ha experimentado un notable desarrollo en las últimas décadas, en
especial las reacciones de carbociclación intramolecular de alenos catalizadas por metales de
transición.1 Por otro lado, de entre la enorme variedad de estructuras heterocíclicas, aquellas
que contienen un núcleo -lactámico y/o indólico son particularmente relevantes debido a su
presencia en productos naturales y sintéticos con actividad biológica.2 Continuando con
nuestro estudio sobre heterociclos y química de alenos,3 se describe la reacción de
carbociclación de alenos catalizada por oro (I) para la preparación de híbridos 2–
azetidinona/indol que contienen un ciclo de tamaño medio.
•
O
cat. Au(I)
N
H H
O
N
N
reflujo
O
O
R
MeO
H H
•
O
N
R
R
cat. Au(I)
N
N
OH H
N
t.a.
R
O
NHR
cat. Au(I)
MeO
N
H H
N
MW
O
R
R
MeO
H H
cat. Au(I)
N
MeO
MW
N
O
H H
N
N
O
•
1
1 (a) Alcaide, B.; Almendros, P. Acc. Chem. Res. 2014, 47, 939. (b) Progress in Allene Chemistry; Alcaide, B.;
Almendros, P., Eds.; Chem. Soc. Rev. 2014, 43, nº 9, 2879-3206.
2 Para la relevancia de -lactamas véanse: (a) Southgate, R.; Branch, C.; Coulton, S.; Hunt, E. Curr. Org.
Chem. 2002, 6, 245. (b) Veinberg, G.; Vorona, M.; Shestakova, I.; Kanepe, I.; Lukevics, E. Curr. Med.
Chem. 2003, 10, 1741. Para la relevancia de indoles véanse: (c) Sundberg, R. J. Indoles; Academic Press:
New York, 1996. (d) Gribble, G. W. J. Chem. Soc., Perkin Trans. 1 2000, 1045.
3 (a) Alcaide, B.; Almendros, P.; Cembellín, S.; Martínez del Campo, T.; Fernández, I. Chem. Commun. 2013,
49, 1282. (b) Alcaide, B.; Almendros, P.; Alonso, J. M.; Cembellín, S.; Fernández, I.; Martínez del Campo,
T.; Torres, M. R. Chem. Commun. 2013, 49, 7779. (c) Alcaide, B.; Almendros, P.; Quirós, M. T.; Chem. Eur.
J. 2014, 20, 3384.
Bilbao, 4-7 Noviembre 2014
Modulación de la Luminiscencia en Nuevos Compuestos Ciclometalados de
PtII y PtIV
Nora Giménez, Jesús R.Berenguer, Julio Fernández, Elena Lalinde, M. Teresa Moreno,
Santiago Ruiz
Departamento de Química, Centro de Síntesis de Química de La Rioja (CISQ), Universidad de la Rioja, 26006,
Logroño, España
[email protected]
En los últimos años los compuestos ciclometalados de PtII han atraído un notable interés
debido a sus potenciales aplicaciones en la fabricación de diodos emisores de luz (OLED),
sensores luminiscentes moleculares, marcadores biológicos y fotocatálisis. Sin embargo, a
pesar de que los compuestos de PtIV exhiben interesantes aplicaciones como anticancerígenos
y catalizadores, los estudios relativos a sus propiedades luminiscentes son escasos comparado
con los llevados a cabo en numerosos derivados de otros iones d6 como ReI, RuII, OsII y IrIII.
En el área de compuestos cicloplatinados, nuestro grupo de investigación ha publicado
numerosos estudios de luminiscencia de materiales de PtII mono y polimetálicos, analizando
la influencia de los ligandos ciclometalados y los coligandos en sus propiedades fotofísicas.1,2
También se han descrito recientemente algunos derivados de PtIV obtenidos por reacciones de
oxidación a partir de compuestos de PtII, pero estos compuestos han resultado ser no
emisivos.3
Continuando nuestro interés en el estudio de compuestos de PtIV, en este trabajo se describe
una nueva ruta para la obtención de compuestos homolépticos de Pt IV con dos ligandos
ciclometalados, [Pt(C^N)2(C6F5)Cl], preparados por oxidación de compuestos de PtII que
tienen un ligando ciclometalado y otro ligando coordinado a través del nitrógeno,
[Pt(C^N)(HC^N)(C6F5)], (C^N= bzq, bt, thpy, pq). La sustitución del cloro en los compuestos
tipo [Pt(C^N)2(C6F5)Cl] por ligandos neutros (4-Mepy, bpe) o aniónicos (CN-) nos ha
permitido sintetizar nuevos derivados de PtIV. Los estudios fotofísicos tanto de los
compuestos de PtIV como de sus precursores de PtII muestran que las propiedades emisivas
dependen del estado de oxidación del metal, del tipo de ligando ciclometalado y de los
coligandos. Además, se ha confirmado la estructura de algunos de estos derivados por
difracción de Rayos X.
II
PtIV
Pt
IV
Pt
IV
Pt
1,0
Intensidad de luminiscencia (u.a.)
PtII
0,8
0,6
0,4
0,2
0,0
300
400
500
600
700
 (nm)
Figura 1
________________________________________________
1 A. Díez, E. Lalinde, M. T. Moreno, Coord. Chem. Rev. 2011, 255, 2426.
2 J. R. Berenguer, A. Díez, E. Lalinde, M. T. Moreno, S. Ruiz, S. Sánchez, Organometallics 2011, 30, 5776.
3 J. R. Berenguer, J. Fernández, N. Giménez, E. Lalinde, M. T. Moreno, S. Sánchez. Organometallics 2013,
32, 3943.
Estudios sobre Nuevos Nanovectores para el Transporte Inteligente de
Medicamentos
Victoria Valdivia,a,b Noureddine Khiar,b Juan José Cid,b e Inmaculada Fernándeza
a
Departamento de química Orgánica y Farmacéutica. Facultad de Farmacia. Universidad de Sevilla. C/
Profesor García González 2. 41012-Sevilla (España). bInstituto de Investigaciones Químicas. Consejo superior
de Investigaciones Científicas. Avda. Américo Vespucio 49. 41092 Sevilla (España)
[email protected]
La autoasociación o autoorganización supramolecular de monómeros mediante enlaces de
tipo electrostático, Van der Waals o enlace de hidrógeno, es actualmente una de las
aproximaciones más potentes y prometedoras de la nanotecnología para la construcción de
nanomateriales funcionales complejos,1 siendo de sumo interés, por ejemplo, en el diseño de
sistemas de transporte inteligente de medicamentos para el tratamiento selectivo del cáncer y
otras enfermedades graves.
El objetivo de nuestro trabajo reside en estudiar la posibilidad de transportar selectivamente
el anticanceroso insoluble en agua sorafenib® a células cancerosas.
Siguiendo un método que consiste en la síntesis de neoglicolípidos diacetilénicos como
monómeros, con un balance hidrófilo-hidrófobo adecuado (Figura 1, compuesto I) hemos
podido obtener, mediante autoorganización supramolecular en gua, sistemas nanométricos
como micelas, liposomas,2 hidrogeles3 y nuevos nanomateriales en forma de disco llamados
gliconanosomas,4 así como caracterizarlos y estudiar algunas de sus aplicaciones.
En esta comunicación, comentaremos los resultados obtenidos en el uso de las micelas,
liposomas y gliconanosomas para la formación de complejos de inclusión con sorafenib® y su
uso para la aniquilación selectiva de células tumorales.
Figura 1.
1 N. Khiar, M. Pernia Leal, R. Baati, C. Ruhlmann, C. Mioskowski, P. Schultz, I. Fernández. Chem.
Commun. 2009, 4121.
2 M. P. Leal, M. Assali, I. Fernández, N. Khiar. Chem. Eur. J. 2011, 17, 1828.
3 M. Assali, J.-J. Cid; I. Fernández, N. Khiar. Chem. Mater. 2013, 25, 4250.
4 M. Assali, M. Pernía-Leal, J.-J. Cid; M. Muñoz, I. Fernández, R. Wellinger, N. Khiar. ACS Nano, 2013, 7,
2145.
Bilbao, 4-7 Noviembre 2014
Síntesis y Propiedades Quirópticas de Ferroceno-Helicenos
Ana M. del Hoyo, Antonio Urbano, M. Carmen Carreño
Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, E-28049
Madrid (España)
[email protected]
Los helicenos1 son benzólogos del fenantreno que se caracterizan por poseer anillos
aromáticos orto-fusionados. La estructura helicoidal es consecuencia de las interacciones
estéricas repulsivas entre los anillos terminales. Estas moléculas son quirales, y dependiendo
de la barrera de interconversión, se pueden resolver en sus dos enantiómeros P y M. Presentan
aplicaciones de interés en campos como la catálisis asimétrica, 2 reconocimiento molecular3 y
nuevos materiales.4
La alta estabilidad del ferroceno, sus propiedades electroquímicas y versatilidad sintética han
hecho que sus derivados encuentren aplicación en diferentes áreas como la catálisis, la
biología5 y la ciencia de materiales. Adicionalmente, los ferrocenil derivados han sido
empleados en el estudio del fenómeno de comunicación electrónica.6 El auge por el desarrollo
de derivados de ferroceno donador-aceptor reside en sus posibles aplicaciones en electrónica
molecular y optoelectrónica.
En este trabajo se ha desarrollado la síntesis de diferentes ferrocenos helicoidales
enantiopuros, donde el resto dador de ferroceno forma parte de la estructura helicénica, o bien
está conectado a través de un enlace covalente. Asimismo, las propiedades quirópticas y
electrónicas de estos sistemas han sido estudiadas mediante dicroísmo circular y voltametría
cíclica.
Figura 1
Agradecimientos: Este trabajo ha sido financiado por el Ministerio de Economía y
Competitividad (Proyecto CTQ2011-24783). A.M.H.. agradece la beca FPU concedida por
MEC en el año 2009.
1 A. Urbano, Angew. Chem. Int. Ed. 2003, 42, 3985; A. Urbano, M. C. Carreño, Org. Biomol. Chem., 2013, 11,
699
2 J. Chen, B. Captain, N. Takenaka, Org. Lett. 2011, 13, 1654.
3 K. Shinohara, Y. Sannohe, S. Kaieda, K. Tanaka, H. Osuga, H. Tahara, Y. Xu, T. Kawase, T. Bando, H.
Sugiyama, J. Am. Chem. Soc. 2010, 132, 3778.
4 H. Oyama, K. Nakano, T. Harada, R. Kuroda, M. Naito, K. Nobusawa, K. Nozaki, Org. Lett. 2013, 15, 2104.
5 D. R. van Staveren, N. Metzler-Nolte, Chem. Rev. 2004, 104, 5931.
6 A. Hilderbrandt, H. Lang, Organometallics 2013, 32, 5640.
The Prediction of Spectroscopic Parameters of Microsolvated Clusters
P. Pinacho, J. C. López, S. Blanco
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid,
47011 Valladolid, Spain.
[email protected]
A molecule is considered to be microsolvated when it is surrounded by a reduced number of
water molecules.This environment, which represents the transition between the isolated and
solvated molecule, can be created in supersonic jets where the microsolvated molecule can be
analysed using different spectroscopic methods. The conformational space of such clusters is
rather complex given the double character proton acceptor/proton donor of water, especially
for biomolecules or biomolecular models which, in turn, may have different stable conformers
or binding sites.One of the mayor difficulties for those studies is to predict the plausible
conformations before starting the experimentation, because there are no structural models for
such kind of systems.The use of “ab initio” methods for this purpose have been generalized,
because they allow exploring the topography of the potential energy surface of those
complexes, giving the values of spectroscopic parameters. In this context, some of the most
used methods and basis sets in Computational Chemistry have been combined, to obtain a
wide selection of levels of theory to be tested against different microsolvated clusters already
observed. The spectroscopic parameters used as key-parameters to predict the rotational
spectra are the rotational constants.
Bilbao, 4-7 Noviembre 2014
Novel Bodipy-Ruthenium Dyads for Homogeneous Photochemical
Oxidations
P. Farràs, T. Madeira, H. Lemmetyinen, N. V. Tkachenko and A. C. Benniston
School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK.
[email protected]
Natural systems are often the main focus of inspiration for scientists. Nowadays, there is a
great deal of research based on mimicking what nature has developed over millions of years.
One field of study is photosynthesis which is the process where plants and other organisms
convert light energy into chemical energy which they use to fuel their activities. The essential
point is that natural systems make use of the cheapest “reagents” available, sunlight and
water. With mankind’s growing demand for energy, attention has turned to nature’s way to
generate energy. The complex machinery of the photosynthetic apparatus serves to harvest
sunlight and direct the resultant excitation energy to a reaction centre. There are numerous
examples of light-harvesting sensitizers, some of them being very complicated molecules. At
first glance, the molecules present in the natural light harvesting system (PSII) are quite
simple. What gives them the almost 100% quantum efficiency to convert photons to electrons
is the supramolecular organization of simple building blocks. Moreover, the electron transport
chain prevents recombination by moving the charges far apart from each other.
Photoelectrochemical cells can be used for artificial photosynthesis as demonstrated by
Fujishima and Honda.1 The light-harvesting and electron transport system can be mimicked
by using photoanodes with molecular sensitizers and semiconductors. Mimicking this primary
charge-separation process in custom-built molecular systems has been intensely studied over
many years.2 Borondipyrromethene (BODIPY) has been shown to be a promising candidate
as sensitizer due to its light absorption and charge transfer properties when coupled to an
electron acceptor.3 Our work has focused on developing simple dyads as sensitizers where,
upon excitation, energy transfer events end up with electrons injected on the semiconductor
and a positive charge located at a BODIPY unit. The synthesis and characterization of dyads
is presented with the properties of these dyes studied by UV absorption, fluorescence
spectroscopy, electrochemistry, transient absorption spectroscopy and surface binding
measurements. Preliminary tests on water oxidation using sacrificial reagents are presented
for both the homogeneous and heterogeneous systems.
Figure 1
1 Fujishima, A.; Honda, K. Nature 1972, 238, 37.
2 Colvin, M. T.; Butler Ricks, A.; Scott, A. M.; Co, D. T.; Wasielewski, M. R. J. Phys. Chem. B 2012, 116,
1923.
3 Benniston, A.C.; He, X.Y.; Lemmetyinen, H.; Tkachenko, N. V. RSC Advances 2013, 3, 4995.
How DNA Interacts with Proteins? A NCI Study of Different DNA BaseAmino Acid Systems
J. González,a I. Baños,b J. Contreras-García,c J. A. Fernándeza and J. Millánb
a
Dpto. Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco-UPV/EHU, Bº Sarriena
s/n, Leioa 48940, Spain. Fax: +34946013500; Tel: +34946015387. bDpto. Química, Facultad de Ciencias,
Estudios Agroalimentarios e Informática, Universidad de La Rioja, Madre de Dios, 51, Logroño 26006, Spain.
c
UPMC, Laboratoire de Chimie Théorique and CNRS, UMR 7616, 75252 Paris Cedex 05, Paris, France
[email protected]
Interactions between DNA and proteins are very common in several biological processes in
the cell.1 In fact, interactions between DNA and histones are the key in the process of the
nucleosome formation.2 But the molecular mechanism that governs that process is not clear.
Studies about the contact propensities between DNA basis and histones show large variations
in the frequency of DNA base-amino acid contacts, depending on the nature of the amino
acid.3 Such differences may be a simple statistical question or may be pointing to the
existence of a specialized language for the DNA-histone interaction, in which non-covalent
interactions are essential.
We will present a systematic study on the conformational behaviour and the nature of several
interactions in DNA – protein systems using quantum chemistry. Applying a reductionist
approach, protein – DNA systems were divided in amino acid – DNA base pairs in order to
reduce the complexity of the system. Then, an exhaustive exploration of the conformational
landscape was carried out using molecular mechanics (MMFFs) followed by DFT
calculations (M06-2X/6-31+G(d) and M06-2X/6-311++G(d,p) on the most stable structures
found.4-5 Finally, the non-covalent interactions were studied with the NCI method6 to
highlight the nature of the interactions. We will present the results obtained for complexes
between Alanine, Valine, Isoleucine, Asparagine, Glutamine and Arginine and a DNA base
(1-methylcytosine or 9-methyladenine) using the above-described methodology.
________________________________________________
1
2
3
4
5
6
D.L.Nelson and M.M. Cox, in Lehninger Principles of Biochemistry, Worh, New York, 2000
J.A. Downs, M.C. Nussenzweig and A. Nussenzweig, Nature 2007, 447, 951-957
S. Jones, P. van Heyningen, H.M. Berman and J.M. Thornton, J. Mol. Biol. 1999, 287, 877-896
T.A. Halgren, J. Comput. Chem. 1999, 20, 730-748
Y. Zhao and D.G. Truhlar, Acc. Chem. Res. 2008, 41, 157-167
R. Chaudret, B. de Courcy, J. Contreras-García, E. Gloaguen, A. Zehnacker-Rentier, M. Mons and J.-PPiquemal, Phys. Chem. Chem. Phys. 2014, 16, 9876-9891
Bilbao, 4-7 Noviembre 2014
Procesos de Transferencia de Oxígeno Catalizados por Complejos de
Dioxomolibdeno(VI): Aplicación a la Síntesis Orgánica
Rubén Rubio-Presa, Nuria García, Patricia García-García, Manuel A. Fernández-Rodríguez,
Cintia Virumbrales, Mª Remedios Pedrosa, Francisco J. Arnáiz y Roberto Sanz*
Departamento de Química, Universidad de Burgos, Pza. Misael Bañuelos s/n, 09001-Burgos
[email protected], [email protected]
Continuando con nuestro interés en el desarrollo de metodologías sintéticas
medioambientalmente benignas que implican procesos redox, empleando como catalizadores
complejos de dioxomolibdeno(VI), recientemente hemos desarrollado un nuevo método que
emplea dimetilsulfóxido (DMSO) como agente de oxidación para la ruptura oxidante de 1,2dioles (Esquema 1).
Esquema 1
Previamente, habíamos descrito la reducción de derivados nitroaromáticos utilizando pinacol
como agente reductor estequiométrico (Esquema 2).1 Teniendo en cuenta ambos resultados,
actualmente nos encontramos estudiando estos procesos de reducción de compuestos
nitroaromáticos con otro tipo de 1,2-dioles. Nuestro propósito es la captura del compuesto
carbonílico, generado como subproducto de la reducción, por parte de las anilinas, formadas
por reducción de los compuestos nitroaromáticos. De esta manera, se podría obtener una
variedad de productos nitrogenados derivados de las correspondientes iminas.
Esquema 2
Agradecimientos: R. R. P. agradece a la Universidad de Burgos su contrato predoctoral.
1 García, N.; García-García, P.; Fernández-Rodríguez, M. A.; Rubio, R.; Pedrosa, M. R.; Arnáiz, F. J., Sanz, R.
Adv. Synth. Catal. 2012, 354, 321.
Recognition of Tumor Associated Glycopeptides by a Potential Sensor
Lectin
David Madariaga, Alberto Avenoza, Jesús Héctor Busto, Francisco Corzana y Jesús Manuel
Peregrina
Departamento de Química, Universidad de La Rioja, Centro de Investigación en Síntesis Química, Logroño,
Spain
[email protected]
MUC1 mucin consists of numerous tandem repeats of the sequence AHGVTSAPDTRPAPG
STAPP that embodies five potential glycosylation points and three important epitopes: the
GVTSA sequence, which is a substrate for GalNAc-transferases, PDTRP fragment that is
recognized by several antibodies and GSTAP which when it is glycosylated the affinity
between the mucin and the antibody increases.1 Besides, Tn antigen (-O-GalNAc-Ser/Thr),
present in aberrantly glycosylated MUC1, is a convenient cancer biomarker that can be
recognized by monoclonal antibodies and lectins.
Taking into account that lectins have been successfully used to recognize malignant tumors,
we have investigated the recognition of MUC1 derivatives by Soybean lectin. This work
yields remarkable results in term of recognition and reveals that this receptor shows higher
affinity to Tn antigen when it is placed at the PDTR peptide region of mucin MUC1. In
contrast, a significant affinity loss is observed when Tn antigen is located at the AHGVTSA
or GVTSA fragments of MUC1 (Figure 1).2
A reasonable explanation of this result was inferred from a study that involves enzyme-linked
lectin assays (ELLA), isothermal titration microcalorimetry (ITC), Saturation-Transfer
Difference (STD)-NMR experiments, Molecular Dynamics (MD) simulations and X-ray
structures.
Figure 1: small glycopeptides synthesized and studied in this work that contain the three
relevant epitopes of mucin MUC1
1 Wilson, R. M.; Danishefsky, S. J. J. Am. Chem. Soc. 2013, 135, 14462.
2 Madariaga, D.; Martínez-Sáez, N.; Somovilla, V. J.; García-García, L.; Berbis, M. Á.; Valero-Gónzalez, J.;
Martín-Santamaría, S.; Hurtado-Guerrero, R.; Asensio, J. L.; Jiménez-Barbero, J.; Avenoza, A.; Busto, J. H.;
Corzana, F.; Peregrina, J. M. Chem. Eur. J., 2014, in press.
Bilbao, 4-7 Noviembre 2014
Propiedades Electroquímicas y Fotofísicas de Compuestos Organometálicos
de Au(I) y Au(III) con el Ligando 2,2´:6´,2´´-Terpiridina
Elena Manso,a M.Concepción Gimeno,b José M. Lopez-de-Luzuriaga,a Miguel Monge,a M.
Elena Olmos,a Gregory G. Wildgoose,c
a
Departamento de Química, Universidad de La Rioja-CISQ, Complejo Científico-Tecnológico, 26004 Logroño,
España. bDepartamento de Químiza Inorgánica, Universidad de Zaragoza-CISQ, Facultad de Ciencias, 500009
Zaragoza, España. cSchool of Chemistry, University of East Anglia, NR4 7TJ Norwich, Reino Unido
[email protected]
En los últimos años los ligandos N-dadores aromáticos han sido uno de los más empleados en
la química de la coordinación del oro, no sólo debido a las características estructurales que
confieren a los compuestos que forman, sino también por la posibilidad de promover nuevas
propiedades fotofísicas y electroquímicas en los compuestos formados.1,2
Dentro de este tipo de ligandos, el ligando terpiridina constituye una molécula de gran interés,
ya que puede inducir tanto propiedades fotofísicas como redox a complejos de oro en
diferentes estado de oxidación. Además, desde el punto de vista estructural se conocen
ejemplos de terpiridinas actuando como ligandos mono-, bi- o tridentados.3
En esta comunicación se presenta la síntesis, caracterización espectroscópica y el estudio
fotofísico (Figura 1) y electroquímico de compuestos organometálicos de oro en estados de
oxidación (I) y (III) coordinados al ligando 2,2´:6´,2´´-terpiridina. Se ha estudiado el
comportamiento de estos compuestos en disolución y en estado sólido, y se ha llevado a cabo
la interconversión entre los complejos de Au(I) y Au(III) tanto química como
electroquímicamente (Figura 2).
Figura 1: Excitación y emisión en estado
sólido a 77K de [Au(C6F5)(terpy)]
Figura 2: Síntesis electroquímica del
complejo [Au(C6F5)(terpy)]2
Agradecimientos: MINECO por la financiación del Proyecto (CTQ 2013-48635-C2-2-P).
Ministerio de Educación por la beca predoctoral FPU a Elena Manso.
________________________________________________
1 Fernández E.J; Laguna A.; López-de-Luzuriaga J. M.; Monge M.; Montiel M.; Olmos M. E.; Pérez J.;
Rodriguez-Castillo M. Gold Bulletin 2007, 40, 172.
2 Bojan V. R.; López-de-Luzuriaga J. M.; Manso E.; Monge M.; Olmos M. E. Organometallics 2011, 30,
4486.
3 Aguado J. E.; Calhorda M. J.; Gimeno M. C.; Laguna. A. Chemical Communications 2005, 3355 and
references therein.
Optimization via Microwave of Conjugation of Magnetic Nanoparticles
with Organic Molecules
Susana Gutiérrez, M. Neus Piña and Jeroni Morey
Departament of Chemistry, Universidad de las Islas Baleares. Cra. de Valldemossa, km 7.5. Palma (Illes
Balears)
[email protected]
A new technique of synthesis and conjugation of organic molecules upon the surface of
magnetic nanoparticles (NP-Fe3O4) was developed in the presence of a microwave reactor.
This technique is based on the vibrations that occur between molecules to affect this radiation
on them, also it has a sealed reaction system resulting cleaner and with higher chemical yields
faster reaction.
A two-step reaction was performed with NP-Fe3O4, in the first-step a substitution reaction
between oleic acid and a linker molecule (APTES ((3-Aminopropyl)triethoxysilane)). In the
second-step is performed a reaction of amide formation. Microwave radiation increases the
nucleophilic attack of the amine to the carboxyl group (determining step in the reaction yield).
Molecules of biological interest like raltitrexed, pemetrexed, methotrexate, folic acid and
DMSA, were used in this project. It was observed a better dispersion in an aqueous medium
for NP-Fe3O4 with amides on the surface. Solubility in aqueous medium is greater by the
number of amide bonds versus the free amines.
Resulting NP-Fe3O4, were characterized by FTIR, Mass Spectrometry and Transmission
Electron Microscopy (TEM). The number of substituents present on the surface of NP-Fe3O4,
was determined by a quantitative analytical assay based on UV-Vis spectroscopy possible to
determine an average of 1000 ligands on the surface of NP of 9 nm in diameter. Scheme 1
shows a general reaction.
Scheme 1: General scheme of the two-step conjugation reaction on the NP-Fe3O4 surface,
performed in a microwave reactor.
An acknowledgment to Fundación Carolina for the fellowship for a master degree, during
which this research was carried out. To CONACyT (Consejo para la Ciencia y la Tecnología
de México) for the fellowship for a PhD.
Bilbao, 4-7 Noviembre 2014
Gold(I)-Catalyzed Cycloisomerizations and Alkoxycyclizations of o(Alkynyl)styrenes
Ana M. Sanjuán, Patricia García-García, Manuel A. Fernández-Rodríguez, Roberto Sanz
Área de Química Orgánica, Departamento de Química, Facultad de Ciencias, Universidad de Burgos,
Pza. Misael Bañuelos s/n, 09001-Burgos, Spain
[email protected], [email protected]
Indenes and related polycyclic structures have been efficiently synthesized by gold(I)catalyzed 5-endo-dig cycloisomerizations and alkoxycyclizations of appropiates o(alkynyl)styrenes. The synthesis of 1H-indenes from o-(alkynyl)styrenes disubstituted at the
terminal position of the olefin allows access to chiral indenes with good enantioselectivities
by using a chiral gold complex as catalyst (A).1 Moreover, dihydrobenzo[a]fluorenes can be
obtained from substrates bearing a secondary alkyl group at the β-position of the double bond
by a tandem gold-catalyzed cycloisomerization/1,2-hydride migration (B).2 Furthermore,
oxygen-functionalized 1H-indenes are obtained by related gold-catalyzed alkoxycyclizations
also in good yields and enantioselectivities (C). In addition, diverse polycyclic compounds are
obtained by intramolecular gold-catalyzed alkoxycyclizations (C). Interestingly, a switch in
the selectivity of the cyclization of o-(alkynyl)-α-methylstyrenes from 6-endo to 5-endo is
observed by adding methanol to the reaction media (D). Therefore, indenes bearing a
quaternary carbon center at C1 can be synthesized.
Scheme 1
1 Martínez, A.; García-García, P.; Fernández-Rodríguez, M. A.; Rodríguez, F.; Sanz, R. Angew. Chem. Int. Ed.
2010, 49, 46334637.
2 García-García, P.; Rashid, M. A.; Sanjuán, A. M.; Fernández-Rodríguez, M. A.; Sanz, R. Org. Lett., 2012,
14, 47784781.
-Dimerization of Oligothienoacene Radical Cations
M. Carmen Ruiz Delgado,a C. Capel Ferrón,a M. Capdevila-Cortada,b Juan J. Novoa,b F.
Hartl,c V. Hernández,a J. T. López Navarretea
a
Departamento de Química Física, Facultad de Ciencias, Universidad de Málaga (Spain). bDepartamento de
Química Física, Facultad de Química, Universidad de Barcelona (Spain). cDepartment of Chemistry, University
of Reading, Whiteknights, Reading RG6 6AD (UK)
[email protected]
Oligothienoacenes, the fused-ring analog of -linked oligothiophenes, belong to the most
promising candidates for organic electronic applications. This is in part due to their densely
packed solid-state structures resulting in high charge carrier mobilities.1 In recent years, there
has been a growing interest in the study of the -dimerization of conjugated radical cations
with a dual purpose: (i) elucidation of the nature of the charge-transport phenomena in doped semiconducting polymers and (ii) development of supramolecular bonding ideas for
applications in material science.2 However, the π-dimerization of planar conjugated radical
cations in solution is scarce and usually encountered at low temperatures. In this work, the
exceptional -dimerization capability showed by radical cations of oligothienoacenes is
investigated for the first time. To this end, we make use of a joint experimental and theoretical
approach that combines different spectroscopic techniques with advanced DFT calculations.
Our results evidence that the incorporation of bulky TIPS groups prevents the -dimerization
while the ,-substitution with n-decyl groups in heptathienoacene or -substitution with
thienyl groups in tetrathienoacene favors the -dimer formation.3 The nature, structure and
stability of the different aggregate structures formed in the course of the oxidation are
rigorously analyzed with the help of exhaustive DFT and TD-DFT calculations.
Scheme 1: a schematic structure of a heptathienoacene -dimer dication and its HOMO
orbital computed at the M06L/6-31G* level.
Acknowledgments: M.C.R.D. thanks the MICINN for a “Ramón y Cajal” Research contract.
______________________________________________
1 Zhang, X.; Côté, A.P.; Matzger, A.J. J. Am. Chem. Soc. 2005, 127, 10502.
2 E. Smela, Adv. Mater. 2003, 15, 481.
3 (a) Capel Ferrón, C.; Ruiz Delgado, M. C.; Hernández, V.; López Navarrete, J.T.; Vercelli, B.; Zotti, G.;
Capdevila-Cortada, M.; Novoa, J.J.; Niu, W.; He, M.; Hartl, F. Chem. Commun., 2011, 47, 12622. (b)
Rizalman, N.S.; Capel Ferrón, C.; Niu, W.; Wallace, A.L.; He, M.; Balster, R.; Lampkin, J.; Hernández, V.;
López Navarrete, J.T.; Ruiz Delgado, M.C.; Hartl, F. RSC Advances 2013, 25644; c) Capel Ferrón, C.;
Capdevila-Cortada, M.; Balster, R.; Hartl, F.; Niu, W.; He, M.; Novoa, J.J.; López Navarrete, J.T.;
Hernández V.; Ruiz Delgado, M.C. Chem. Eur. J., 2014, 20, 10351.
Bilbao, 4-7 Noviembre 2014
Fluorescent Pyrene-based Azole Compounds: Synthesis and Photophysical
Analysis
Susana Ibáñez, Macarena Poyatos, Eduardo Peris
Dpto. de Química Inorgánica y Orgánica, Universitat Jaume I, Avda. Sos Baynat s/n, 12071-Castellón (Spain)
[email protected]
We have recently demonstrated that mono-1 and bis-imidazolium2 salts decorated with a
polyaromatic ring such as pyrene exhibit interesting fluorescence properties. Keen to further
explore the photophysics and applications of these pyrene-based azole compounds, a
systematic series of these materials has been prepared and studied.
The neutral compounds 1, isolated as a mixture of the syn and anti isomers (only the anti
isomers are depicted in Scheme 1), show a violet structured band (max = 378 nm) with
vibronic spacing (1300-1455 cm-1) and emission quantum yields (f) about 0.50.
Subsequent alkylation of compounds 1 with different alkylating agents afforded symmetrical
and unsymmetrical bis-imidazolium salts 2. All bis-azolium salts show fluorescence
properties, with emission at 372 nm with vibronic spacing (1297-1370 cm-1) and high f
values. Interestingly, charged moieties are embodied within the system of cromophores 2,
which distinguishes these materials from common types of fluorescent organic salts.
Metal complexes bearing a high field strength ligand such as an N-heterocyclic carbene
(NHC) give rise to high energy emissions, and consequently, feature multiple applications in
the design of optical devices and organic light emitting diodes (OLEDs).3 In this context, salts
2 have been used as bis-NHC precursors in the preparation of a series of Pt(II) complexes,
bearing a phenylpyridine ligands. The study of their photophysical properties is currently
underway.
Scheme 1
Acknowledgements: we gratefully acknowledge financial support from Ministerio de
Economía y Competitividad of Spain (CTQ2011-24055/BQU) and Universitat Jaume I (VAL2013-01). We also are grateful to the Ramón y Cajal program (M.P.).
1 Gonell, S.; Poyatos M.; Peris E. Chem. Eur. J. 2014, 20, 9716-9724
2 H. Valdes, M. Poyatos, E. Peris, Organometallics 2014, 33, 394
3 Visbal, R.; Gimeno, M.C. Chem. Soc. Rev., 2014, 43, 3551
NHCs Bearing a Chelating Scaffold as Supporting Ligands for Iron
Complexes
Mònica Rodríguez, David Font, Julio Lloret and Miquel Costas
Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona,
Campus Montilivi, 17071, Girona (Spain)
[email protected]
The use of N-Heterocyclic Carbenes (NHCs) as supporting ligands for transition metal
complexes has become important in the recent years. Their utility relies on their strong σdonation property, which can give rise to strong M-C bonds, generating catalysts resistant
towards decomposition and that can stabilize high-valent intermediates. Moreover, their
electronic and steric properties can be easily tuned, what is highly desirable in coordination
chemistry. And among to their inherent advantages, the complex stability and reactivity can
be modulated by adding in the NHC structure a chelating scaffold.1
Different NHC complexes have been extensively studied using different metal centers, such
as Pd and Rh. Nevertheless, Fe-NHC complexes have been unexplored for a long period of
time due to the difficulty of its synthesis. However, the desirable use of these iron complexes
as catalyst arises from the combination of the advantages of NHCs as ligands and the use of
iron as an environmentally benign metal center. For this reason, different applications of these
iron catalysts have been already described.2
Herein, we present the synthesis of new carbene ligands incorporating a chelating scaffold of
a 1,4-dimethyl-1,4,7-triazacyclononane moiety, which has affinity to coordinate to iron as it
has been studied previously.3 Moreover, the generation of the corresponding Fe-NHC
complexes is also studied.
Figure 1
1 Grohmann, C.; Hashimoto, T.; Fröhlich R.; Ohki, Y.; Kazuyuki, T.; Glorius, F. Organometallics 2012, 31,
8047.
2 Riener, K.; Haslinger, S.; Raba, A.; Högerl, M. P.; Cokoja, M.; Herrmann, W. A.; Kühn, F. E. Chem. Rev.
2014, 114, 5215.
3 a) Prat, I.; Company, A.; Corona, T.; Parella, T.; Ribas, X.; Costas, M. Inorg. Chem. 2013, 52, 9229. (b) Prat,
I.; Company, A.; Postils, V.; Ribas, X.; Que, L. Jr.; Luis, J. M.; Costas, M. Chem. Eur. J. 2013, 19, 6724.
Bilbao, 4-7 Noviembre 2014
A Straightforward Synthesis of Alkynes from Grignard Reagents and
Sulfonylacetylenes
Francisco Esteban, Jose Luis García Ruano, Alberto Fraile and José Alemán
Departamento de Química Orgánica, Universidad Autónoma de Madrid, C/ Francisco Tomás y Valiente, 7,
Cantoblanco 28049 Madrid
[email protected]
Recently, our group has published the anti-Michael addition of organolithium reagents to
arylsulfonylacetylenes,1 giving access to a large variety of alkynes in a very easy manner.
However, the use of organolithium reagents has some limitations such as the use of groups
sensible to these reagents like nitro and esters. On the other hand, lithium organocompounds
are too sensitive to moisture and need extremely hygroscopic conditions and low
temperatures. For this reasons, we thought that the use of magnesium compounds could be a
solution for this new approach for the synthesis of acetylenic fragments.
Taking into account that Grignard reagents are less reactive and, in some cases, more selective
than organolithium compounds,2 we studied the reaction of sulfones with RMgBr, obtaining
alkynyl compounds bearing alkyl, alkynyl and aromatic fragments with donor and
withdrawing substituents, including nitro and ester groups.
Scheme 1
In this communication, we describe the unexpected ¨antiMichael¨addition of Grignard
compounds to arylsulfonylacetilenes, to give the corresponding alkynes under very mild
conditions. The broad scope, good yields, and simplicity of the experimental procedure are
the main features of this methodology. A rational explanation of these results could be the
initial association of the organomagnesium to the electrophile as a previous step, and a
subsequent intramolecular attack giving the final products through an “anti-Michael” reaction.
1 (a) J. L. García Ruano, J. Alemán, L. Marzo, C. Alvarado, M. Tortosa, S. Díaz-Tendero and S. Fraile, Angew.
Chem. Int. Ed. 2012, 51, 2712. (b) J. L. García Ruano, J. Alemán, L. Marzo, C. Alvarado, M. Tortosa, S.
Díaz-Tendero and S. Fraile, Chem. Eur. J. 2012, 18, 8814.
2 (a) P. Knochel, W. Dohle, N. Gommermann, F. F. Kneisel, F. Kopp, T. Korn, I. Sapountzis and V. A. Vu
Angew. Chem. Int. Ed 2003, 42, 4302. (b) H. Ila, O. Baron, A. J. Wagner and P. Knochel Chem. Commun.
2006, 583.
Brønsted Acid-Catalyzed Reaction of Indoles with Acetylenic 1,4-Diols.
Direct Synthesis of 2-Indol-3-ylbenzofulvenes
Estela Álvarez,a Olalla Nieto-Faza,b Carlos Silva,b Claudia Feberero,a Manuel A. FernándezRodríguez,a Roberto Sanza,*
a
Departamento de Química, Facultad de Ciencias, Universidad de Burgos, Pza. Misael Bañuelos s/n, 09001Burgos, Spain. bDepartamento de Química, Universidade de Vigo, Lagoas Marcosende, 36310-Vigo, Spain
[email protected]
A few years ago we developed a robust method for the reaction of indoles with propargylic
alcohols under metal-free Brønsted acid-catalysis that provides a wide variety of 3propargylindole derivatives.1 In addition, these substrates undergo interesting gold(I)catalyzed transformations mainly involving [1,2]-indole migration processes.2 At this point
we thought about the possibility that Brønsted acid could mimic the behaviour of cationic
gold(I) catalysts in order to trigger an intramolecular nucleophilic attack of the indole onto the
alkyne (Scheme 1).
Herein we report that alkynes bearing an indole at one propargylic position and an activated
hydroxyl group at the other propargylic position undergo an unprecedented Brønsted acidcatalyzed cascade sequence leading to 2-indol-3-ylbenzofulvene derivatives. The proposed
mechanism, which likely involves a 1,2-indol-migration followed by a Nazarov cyclization,
has also been supported by DFT calculations.
Scheme 1
1 Sanz, R.; Miguel, D.; Martínez, A.; Gohain, M.; García-García, P.; Fernández-Rodríguez, M.; Álvarez, E.;
Rodríguez, F. Eur. J. Org. Chem. 2010, 70277039.
2 (a) Sanz, R.; Miguel, D.; Rodríguez, F. Angew. Chem. Int. Ed. 2008, 47, 73547357. (b) Sanz, R.; Miguel,
D.; Gohain, M.; García-García, P.; Fernández-Rodríguez, M. A.; González-Pérez, A.; Nieto-Faza, O.; de
Lera, A. R.; Rodríguez, F. Chem. Eur. J. 2010, 16, 98189828.
Bilbao, 4-7 Noviembre 2014
Experimental and Theoretical Approaches to the Influence of the Addition
of Pyrene to a Series of Pd and Ni NHC-Based Complexes. Catalytic
Consequences
Hugo Valdés, Macarena Poyatos* and Eduardo Peris*
Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, Av. Vicente Sos Baynat s/n, 12071
Castellón, Spain
[email protected]
The incorporation of pyrene into N-heterocyclic carbene (NHC) ligands may add interesting
photophysical applications to their derived complexes and may also introduce catalytic
benefits due to its -stacking capabilities. In this regard, we reported a pyrene-based-NHC
ligand and its coordination to Rh and Ir.1 We now report its coordination to Pd and Ni, giving
complexes 6 and 9 respectively (Scheme 1), and the study of their catalytic performances in
the Suzuki-Miyaura cross coupling and in the -arylation of arylketones with arylhalides. For
comparative purposes, we also prepared a series of Pd and Ni complexes bearing other two
NHC ligands, namely, imidazolylidene, benzoimidazolylidene.
By means of 1H-NMR and UV-vis spectroscopies, we have demonstrated that in the presence
of a -stacking additive such as pyrene, the pyrene-based complexes 6 (Pd) and 9 (Ni) result
in an adduct species in which the added pyrene is connected to the metal complexes via stacking interaction with the pyrene group of the ligand. This  stacking interaction gives
rise to a modification of the electronic properties of the metal, as demonstrated by cyclic
voltammetric studies on the Ni-NHC complexes. In order to explore the implications of this
- stacking interaction in catalysis, we study the catalytic behaviour of all the complexes in
the Suzuki-Miyaura coupling and in the -arylation of arylketones with arylhalides, in the
presence of pyrene. The addition of pyrene resulted in a decrease of the catalytic
performances of the Pd complexes in the -arylation of arylketones. On the other hand, the
catalytic studies on the Suzuki-Miyaura cross coupling reactions reveals that the addition of
pyrene did not produce any significant changes. We carried out a theoretical study to
understand this behaviour.
Scheme 1
We gratefully acknowledge financial support from MEC of Spain (CTQ2011-24055/BQU)
and UJI (P1.1B2011-22). We also would like to thank the Santiago Grisolía (H.V.) and
Ramón y Cajal (M.P.) programs.
1 Valdes, H.; Poyatos, M.; Peris, E. Organometallics 2014, 33, 394.
Palladium-catalysed Direct Cross-coupling of Organolithium Reagents with
Aryl and Vinyl Triflates
Carlos Vila,a,b Valentín Hornillos,a Massimo Giannerini,a Martín Fañanás-Mastrala and Ben L.
Feringaa,*
a
Stratingh Institute of Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
b
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, E-46100
Burjassot (València), Spain
[email protected]
The development of new methodologies for transition metal catalysed cross coupling
reactions has attracted the attention of the chemistry community for the past 40 years. 1 In this
context, palladium mediated C-C bond formations, have played a crucial role, and
methodologies involving palladium catalysis for cross-coupling have shown to be particularly
effective. As a consequence Pd-catalysed cross-coupling has found widespread application in
the industrial manufacturing of pharmaceuticals, fine chemicals and materials in the last
decades.
In this communication, we present a palladium catalysed cross-coupling of organolithium2
reagents with a aryl and alkenyl triflates. The reaction proceeds at 50 or 70 °C with short
reaction times, and the corresponding products are obtained with moderate to high yields,
with a variety of alkyl and (heteroaryl)aryl lithium reagents. 3
Scheme 1
The Netherlands Organization for Scientific Research (NOW-CW), National Research School
Catalysis (NRSC-Catalysis), the European Research Council (ERC advanced grant 227897),
the Ministry of Education Culture and Science (Gravity program 024.601035) is gratefully
acknowledged for financial support. C.V. was supported by an Intra-European Marie Curie
fellowship (FP7-PEOPLE-2011-IEF-300826).
1 (a) de Meijere, A.; Diederich, F. in Metal-Catalyzed Cross-Coupling Reactions, Wiley-VCH, Weinheim, 2nd
edn, 2004. (b) Beller, M.; Bolm, C. in Transition Metals for Organic Synthesis, Wiley-VCH Verlag GmbH,
Weinheim, 2nd edn, 2004. (c) Netherton, M. R.; Fu, G. C., in Topics in Organometallic Chemistry:
Palladium in Organic Synthesis, Tsuji, J., Ed., Springer: New York, 2005, 85-108.
2 (a) Giannerini, M.; Fañanás-Mastral, M.; Feringa, B. L. Nat. Chem. 2013, 5, 667-672. (b) Hornillos, V. ;
Giannerini, M.; Vila, C.; Fañanás-Mastral, M.; Feringa, B. L. Org. Lett. 2013, 15, 5114-5117. (c) Giannerini,
M.; Hornillos, V.; Vila, C.; Fañanás-Mastral, M.; Feringa, B. L. Angew. Chem. Int. Ed. 2013, 52, 1332913333. (d) Vila, C.; Giannerini, M.; Hornillos, V.; Fañanás-Mastral, M.; Feringa, B. L. Chem. Sci., 2014, 5,
1361-1367.
3 Vila, C.; Hornillos, V.; Giannerini, M.; Fañanás-Mastral, M.; Feringa, B. L. Chem. Eur. J., 2014, DOI:
10.1002/chem.201404398
Bilbao, 4-7 Noviembre 2014
Analysis of Organic Gunshot Residues by Raman Imaging
María López-López, M. Ángeles Fernández de la Ossa and Carmen García-Ruiz
Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, & University Institute of
Research in Police Sciences, University of Alcalá, Ctra. Madrid-Barcelona km 33.600, 28871 Alcalá de Henares
(Madrid) Spain.
[email protected]
Gunshot residues (GSR) are a set of burned and unburned particles produced when a gun is
fired. As the GSR are transferred to the shooter, the weapon, the victim, or the surrounding
environment, their identification is a crucial part of crime scene investigation. Raman
spectroscopy is a vibrational technique that has emerged as a useful tool to analyze the
organic gunshot residues (OGSR)1,2,3 offering additional information to the technique of
choice for analyzing GSR, the Scanning Electron Microscopy coupled with Energy
Dispersive X-Ray Spectroscopy (SEM-EDX) technique.
A commercial Raman imaging system using an electron multiplying coupled-charged device
(EMCCD) camera, which dramatically reduces the acquisition time, was used to analyze the
OGSR particles from different ammunitions fired on different clothing targets stained with
blood to mimic real-world evidence. The particles collected using SEM-EDX stubs as well as
the direct analysis of the fired clothing targets were measured. Chemical maps and
multivariate curve resolution methods applied to the spectroscopic data confirmed that both
measurement approaches can be used for the identification of OGSR particles even under
unfavorable conditions. The results obtained demonstrate the huge potential of fast Raman
imaging for the analysis of OGSR particles.
1347
(a)
(b)
1283
1407
1592
863
1145
Black
clothing
(c)
OGSR
particle
Raman shift (cm-1)
Fig. 1 (a) Raman spectra of a black clothing and an OGSR particle, (b) microscope image of a
mapped OGSR particle on black cotton clothing and (c) corresponding MCR analysis (blue
color indicates the spectra assigned to the OGSR particle, whereas red color corresponds to
the substrate). Raman conditions: 455 nm, 6.0 mW, 50×, slit size of 50 μm, 0.01 s × 30 scan,
5 μm step sizes, 7857 spectra.
1 López-López, M.; Delgado, J. J.; García-Ruiz, C. Analytical Chemistry 2012, 84, 3581.
2 López-López, M.; Delgado, J. J.; García-Ruiz, C. Forensic Science International 2013, 231, 1.
3 Bueno, J.; Sikirzhytski, V.; Lednev, I. K., Analytical Chemistry 2012, 84, 4334.
Direct Catalytic Cross-Coupling of Organolithium Compounds
Valentín Hornillos, Massimo Giannerini, Carlos Vila, Martín Fañanas-Mastral and Ben L.
Feringa.
Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The
Netherlands.
[email protected]
The development of new catalytic methodologies for carbon-carbon bond formation continues
to be a major challenge in organic synthesis. Cross-coupling reactions, in particular
palladium-catalyzed processes, are among the most important current methods for C-C bond
formation.1 A tremendous effort has been dedicated in the last 40 years to expand the scope of
these methodologies and many organometallic reagents as Grignard, zinc, boron, tin and
silicon reagents were identified as suitable partner in these reactions. Organolithium reagents
in contrast have been scarcely considered due to the difficult control of their reactivity.
Considering the importance of organolithium compounds, a procedure to directly employ this
reagent in coupling reactions is desirable. Herein we report a general methodology for the
cross-coupling of aryllithium with aryl halides that proceeds under mild conditions and in
short reaction times.2 Inspired by the high efficiency of these transformations, we also
developed an expeditious Pd-catalyzed cross-coupling protocol for the synthesis of tri- and
tetra-ortho-substituted biaryls under ambient conditions.3
Scheme 1: palladium catalyzed cross-coupling with aryllithium reagents
The Netherlands Organization for Scientific Research (NWO-CW) and the European
Research Council (ERC advanced grant 227897 to BLF), are acknowledged for financial
support.
1 (a) Negishi, E. Angew. Chem. Int. Ed. 2011 , 50, 6738. (b) Magano, J.; Dunetz, J. R. Chem. Rev. 2011 , 111,
2177.
2 (a) Giannerini, M.; Fañanás-Mastral, M.; Feringa, B. L. Nat. Chem. 2013, 5, 667. (b) Hornillos, V.;
Giannerini, M.; Vila, C.; Fañanás-Mastral, M.; Feringa, B. L. Org lett. 2013 ,15, 5114.
3 Giannerini, M.; Hornillos, V.; Vila, C.; Fañanás-Mastral, M.; Feringa, B. L. Angew. Chem. Int. Ed. 2013 , 52,
13329.
Bilbao, 4-7 Noviembre 2014
Organocatálisis Aplicada a la Reducción Enantioselectiva de Iminas
Empleando Cl3SiH como Reductor
María Maciá, Vicente Martí, Raúl Porcar, Eduardo García-Verdugo, María I. Burguete y
Santiago V. Luis
Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, Avda. Sos Baynat s/n 12071, Castellón,
España
[email protected]
Una transformación comúnmente usada para la obtención de aminas quirales es la reducción
de enlaces imina (C=N). La hidrogenación asimétrica de iminas proquirales permite generar
un nuevo estereocentro. Las aminas quirales forman parte de una gran variedad de moléculas
bioactivas como por ejemplo fármacos o productos naturales1. Es este contexto, nuestro
trabajo se centra en el desarrollo de metodologías que siendo químicamente eficientes sean
respetuosas con el medioambiente. Por ello, nuestros esfuerzos se centran en el diseño de
estrategias sintéticas que permitan su síntesis mediante el uso de organocatalizadores. Es
decir, obtener aminas quirales mediante moléculas orgánicas enantiopuras de bajo peso
molecular, en ausencia de metales. La clave es desarrollar sistemas que siendo altamente
selectivos sean simultáneamente fáciles de obtener, con un coste reducido y benignos desde el
punto de vista medioambiental.
En esta comunicación se presentaran nuestros esfuerzos en la obtención de una mayor
comprensión del mecanismo de acción de las --aminoamidas2 como organocatalizadores en
la reducción de iminas proquirales empleando Cl3SiH como agente reductor mediante
estudios de RMN y cálculos teóricos. Estos estudios sugieren que en el estado de transición el
silicio forma una esfera de coordinación bipirámidal, con seis átomos a su alrededor, en la que
el organocatalizador está coordinado al silicio únicamente por el átomo de nitrógeno.
Esquema 1
Agradecimientos: financiado por GV‐PROMETEO/2012/020,
MICINN_CTQ‐2011‐28903‐C02‐01 y UJI-P1-1B2013-37.
accomp‐GV‐/2013/207,
1 Jones, S.; Warner, C. J. A,, Org. Biomol. Chem, 2012, 10, 2189.
2 Burguete, M. I.; Collado, M.; Escorihuela, J.; Luis, S. V., Angew. Chem. Int. Ed. 2007, 46, 9002.
Molecular Recognition in Sugars by Laser Spectroscopy: Glucose Clusters
Imanol Usabiaga,a Pedro F. Arnaiz,a Jorge González,a Iker León,a Judith Millán,b Emilio J.
Cocinero,a José A. Fernándeza
a
Universidad del País Vasco UPV/EHU Facultad de Ciencia y Tecnología, Barrio Sarriena s/n 48980 Leioa –
Bizkaia. 2 Universidad de La Rioja, Avda. de la Paz, 93, 26006 Logroño, La Rioja
[email protected]
Sugars are essential building blocks in living organisms. Their interactions with other
biological molecules are important for processes such as cell recognition1,2,3 and cell wall
formation. Those interactions take place through weak hydrogen bonds and van der Waals
forces, which are difficult to model. To shed light on how sugar molecules interact here we
present a study of several structures of Phenyl-β and methyl-β,α-glucopyranose aggregated to
phenol (see Figure1). This reductionist approach simulates the interaction with tyrosine, one
of the binding amino acids in proteins. Additionally, complexes consisting of phenyl-β-Dglucopyranose and capped Phenyl-β- and methyl-α-β-D-glucopyranose are studied and
characterized, in order to model the interactions between cellulose chains. Finally a
comparison with the results obtained for the two glucopyranose complexes using non capped
α,β-D-glucopyranose is also presented. The experimental measures were done through laser
spectroscopy in supersonic jet expansion conditions. Comparison of the experimental results
with the theorically simulated vibrational spectra at DFT level allows obtaining structural
information. The results reveal a preferential linking point in Glucopyranose ring due to
cooperative networks of hydrogen bonds.
Figure 1: observed structures of the most stables conformers for Methyl-DGlucopyranose···Phenol complex.
________________________________________________
1 E. J. Cocinero, P. Çarcabal, T. D. Vaden, J. P. Simons and B. G. Davis. Nature; 2011, 469; 7328.
2 A. G. Santana, E. Jimenez-Moreno, A.M. Gomez, F. Corzana, C. Gonzalez, G. Jimenez-Oses, J. JimenezBarbero, J. L.Asensio; J. Am. Chem. Soc., 2013, 135 (9), 3347–3350
3 I. León, J. Millán, E. J. Cocinero, A. Lesarri and J. A. Fernández.; Angew. Chem. Int. Ed. 2013, 52, 77727775.
Bilbao, 4-7 Noviembre 2014
Synthesis of a Mimic of Tn Antigen through a Stereoselevtive sulfa-Michael
Addition
Marta I. Gutiérrez-Jiménez, Carlos Aydillo, Alberto Avenoza, Jesús H. Busto, Francisco
Corzana, María del Mar Zurbano and Jesús M. Peregrina
Departamento de Química, Universidad de La Rioja, Centro de Investigación en Síntesis Química, C/ Madre de
Dios, 51, 26006 Logroño, La Rioja, Spain, phone: +34 941 299630;
[email protected]
It is well-known the important role that glycoproteins and glycopeptides play in many
biological processes. In particular, the significance of S-glycopeptides has been rising during
last years. The incorporation of a sulfur atom instead of oxygen in O-glycopeptides improves
chemical stability, making them more resistant to glycosidases. Moreover, these compounds
are tolerated by most biological systems, i. e. sublancine.1 In this field, we recently reported
the synthesis of new chiral dehydroamino acid derivatives which presented high yields and
stereoselectivities in sulfa-Michael additions with cysteine derivatives2 and protected
thiocarbohydrates,3 allowing the synthesis of lanthionines and sulfa-Tn antigen mimics,
respectively.
In order to extend this methodology, we designed a new chiral bicyclic acrylate derivative (1).
This new compound presented the same reactivity and stereoselectivity of previously reported
precursor.3 This fact was shown when compound (1) was reacted with tri-O-acetyl-2acetamido-2-deoxy-1-thio-α-D-galactose, affording the corresponding sulfa-Michael adduct
(2) as the only diastereoisomer. As a final step, to confirm the stereochemistry of the new
chiral centre generated in the sulfa-Michael reaction, adduct (2) was hydrolyzed in order to
obtain the corresponding free S-glycoamino acid, which can be regarded as a mimic of Tn
antigen, but with (S)-configuration at C of amino acid moiety. Thus, an alternative route to
this important compound has been developed.
Scheme 1
1 Oman, T. J.; Boettcher, J. M.; Wang, H.; Okalibe, X. N.; Van Der Donk, W. A. Nat. Chem. Biol. 2011, 7,
78.
2 Aydillo, C.; Avenoza, A.; Busto, J. H.; Jiménez-Osés, G.; Peregrina, J. M.; Zurbano, M. M. Org. Lett. 2012,
14, 334.
3 Aydillo, C.; Compañón, I.; Avenoza, A.; Busto, J. H.; Corzana, F.; Peregrina, J. M.; Zurbano, M. M., J. Am.
Chem. Soc. 2014, 136, 789.
Novel Metal Complexes Derived from Pseudopeptidic Ligands
Lingaraju Gorla, Vicente Martí, Belén Altava, M. Isabel Burguete and Santiago V. Luis
Departamento de Química Inorgánica y orgánica, Universitat Jaume I, Castellón, 12071, Spain
[email protected], [email protected]
Amino acid derived compounds have recently drawn much attention in very different fields
like synthetic, bioorganic, medicinal, and supramolecular chemistry.1 In this regard, the
design and synthesis of ligands functionalized to achieve metal complexation in a biomimetic
approach is a challenge of current interest.2 The inclusion of amino acid residues in the
structure is one of the most obvious strategies to provide coordination environments of the
metal ions similar to those found in metalloproteins. On the other hand, the presence of
chirality derived from the amino acid subunits allows the potential application in
enantioselective catalysis.
Here, we present the study of the complexation of pseudopeptidic ligands with different
transition metals (Cu, Ni, and Zn) and their crystal structures obtained by X-ray
Crystallography. These complexes have been also studied potentiometrically using 1:1 ligand:
metal ratios.3 These complexes have potential applications for different catalytic reactions like
aldol, henry, opening of epoxides, and formation of polycyclic carbonates.
Scheme 1: structures of the pseudopeptidic metal complexes
Acknowledgements: financial support from Spanish MINECO (CTQ2012-38543-C03-01),
Generalitat Valenciana (PROMETEO/2012/020) and PPI-UJI (P1-1B-2013-38) are gratefully
acknowledged. LG also thanks GV for Santiago Grisolia fellowship (2012/015).
1 Supramolecular Chemistry. Concepts and Perspective, VCH, Weinheim,Germany,1995.
2 H. Miyake, Y. Kojima, Coord. Chem. Rev. 1996, 148, 301-304.
3 Martí, I.; Ferrer, A.; Escorihuela, J.; Burguete, M. I.; Luis, S. V. Dalton Trans. 2012, 41, 6764–6776.
Bilbao, 4-7 Noviembre 2014
Integration of Multicatalytic and Multistep Processes for the Continuous
Flow Synthesis of APIs
Edgar Peris, Raúl Porcar, Eduardo García-Verdugo, M. Isabel Burguete, Santiago V. Luis
Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, Av. de Vicente Sos Baynat, s/n,
Castellón de la Plana, Spain.
[email protected], [email protected]
Many research efforts are driven to the development of more efficient and sustainable
synthetic processes for the preparation of Fine Chemicals and Pharmaceutical products. In
recent years, we have been exploring the use of continuous flow systems based on
functionalized polymers as heterogeneous reagents or catalysts to achieve this goal. The
immobilization of the catalyst onto a polymeric support facilitates the separation and reuse of
the catalyst, providing products not contaminated by elements of the catalytic system, and,
simultaneously, allowing for the implementation of continuous processes.1
The use of a sequential set of mini-reactors under flow conditions allows the integration of
different catalysts to perform multistep synthesis in a single process. It allows the simple
compartmentalization of the different catalytic systems (e.g. sequential catalytic fix-bed
reactors) and enable to operate at different P and T conditions, according to the needs of each
individual step. (see Fig 1).2
Cat-1
I1
MP1
1 Paso
MP2
MP: Material de Partida
I: Intermedio
Cat: catalizador
P: Product
2 Paso
Cat-2
MP3
3 Paso
I2
P
Cat-3
Figure 1: Multireactor network for the synthesis of a product through the integration of three
catalytic steps.
Here, we report our efforts for developing multicatalytic reaction networks for the synthesis
of cyanohydrines, a key intermediates for the preparation of different APIs. Good results were
obtained including long-term catalysts stability and products with high yield and
enantiomerical excess (>99.9 % e.e.).
Ackowledgements: Financial support by MICINN (CTQ, 2011-28903-C02-01 and
FPU13/00685) and GV (PROMETEO/2012/020) and UJI (P1-1B2013-37) are acknowledged.
1 R. Porcar, V. Sans, N. Ríos-Lombardía, V. Gotor-Fernández, V. Gotor, M. I. Burguete, E. García-Verdugo,
S. V. Luis, ACS Catal., 2012, 2, 1976-1983.
2 S. Martín, R. Porcar, E. Peris, M. I. Burguete, E. García-Verdugo, S. V. Luis, Green Chemistry., 2014, 16,
1639-1647.
Purification and Characterization of White Broom (Cytisus multiflorus)
Peroxidase
Patricia Pérez Galende,a C. García de María,b V. Shnyrovc and M. G. Roigd
a
Dpto. de Química Física/ Facultad de Farmacia, Universidad de Salamanca. bDpto. de Química Analítica,
Nutrición y Bromatología/ Facultad de Ciencias Químicas, Universidad de Salamanca. cDpto. de Bioquímica y
Biología Molecular, Universidad de Salamanca. dDpto. de Química Física/ Facultad de Farmacia, Universidad
de Salamanca
[email protected]
White Spanish Broom (Cytisus multiflorus) is one of the most abundant wild bushes in Spain
and Portugal. A new peroxidase has been isolated from this plant and subsequently
characterized. Peroxidases are important enzymes participating in reactions of biological
significance such as cell wall formation, lignification and protection of tissues from
pathogenic microorganisms1. They also have numerous biotechnological applications such as
additives for bioremediation2 or catalysts in the production of conducting polymers3.
Peroxidase from Cytisus multiflorus (CMP) has been purified in a five-step process, namely
homogenization, extraction of coloured compounds and consecutive chromatographic
separations on Phenyl-Sepharose, HiTrapTM SP HP and Superdex-75.
The molecular weight of the enzyme was found to be around 50 kDa and R Z parameter was
2,9. The retention time of the protein when eluted by size-exclusion chromatography indicates
that the dissolved enzyme is monomeric.
The CMP secondary structure and its changes during thermal denaturation processes were
monitored by UV CD. CMP is different from other plant peroxidases because of the native
enzyme contains a considerable amount of β- strands. The T* parameter and the activation
energy for CMP were 337,0 ± 0,8 K and 58,7 ± 1,4 kcal mol-1, respectively.
For the oxidation of guaiacol as cosubstrate, the optimum pH and temperature were 6,0 and
25ºC respectively, and the Michaelian kinetic parameters were Km =3,86 mM and Vmax =
5,42· 10-5 Ms-1.
1 Penel, C.; Gaspar, T.; Greppin, H. Literature on Molecular, Biochemical and Physiological Aspects.
University of Geneva, Switzerland 1992.
2 Adler, P.R.; Arora, R.; Ghaouth, D.M. J. Environ. Qual. 1994, 23, 1113.
3 Caramyshev, A.V.; Evtushenko, E.G.; Ivanov, V.F.; Ros Barceló, A.; Roig, M.G.; Shnyrov, V.L.; Huystee,
R.B.; Kurochkim, I.N.; Vorobiev, A.K.; Sakharov, I.Y. Biomacromolecules 2005, 6, 1360.
Bilbao, 4-7 Noviembre 2014
Aryl -Lithiobenzyl Ethers: Inhibition of [1,2]-Wittig Rearrangement.
Rocío Velasco, Manuel A. Fernández-Rodríguez and Roberto Sanz*
Área de Química Orgánica, Departamento de Química, Facultad de Ciencias, Universidad de Burgos, Pza.
Misael Bañuelos s/n, 09001-Burgos, Spain.
[email protected], [email protected]
The rearrangement of α-alkoxyorganolithiums, usually generated by deprotonation of an
ether, to lithium alkoxides by [1,2]-migration of a C-group from oxygen to carbon is known
as the [1,2]-Wittig rearrangement.1 Among the different mechanisms that have been proposed
for this reaction, a two-step one involving the formation of a pair of radicals and subsequent
recombination (Scheme 1) better accommodates the experimental findings, mainly the
migratory aptitude of the R group, which increases in the following order: prim- < sec- < tertalkyl < benzyl (consistent with the stability order of the corresponding radicals R·).2
However, the migration of aryl groups is not so common and, in addition, an alternative
pathway involving intramolecular nucleophilic addition and terminated by nucleofugal
elimination has also been claimed for lithiated allyl aryl ethers.3
Scheme 1
In this context, we have described that -lithiobenzyl o-lithiophenyl ethers, generated from
benzyl 2-halophenyl ethers, do not undergo the Wittig rearrangement allowing their use in
synthesis by trapping with electrophiles such as carboxylic esters (Scheme 2).4 Herein, we
report that simple aryl benzyl ethers can be selectively deprotonated at the benzylic position
and how a careful control of the temperature reaction allows the generated aryl -lithiobenzyl
ethers to be trapped with selected electrophiles.
Scheme 2
________________________________________________
1 Wittig, G.; Löhmann, L. Justus Liebigs Ann. Chem. 1942, 50, 260268.
2 Tomooka, K.; Yamamoto, H.; Nakai, T. Liebigs Ann./Recueil 1997, 12751281.
3 (a) Eisch, J. J.; Kovacs, C. A.; Rhee, S.-G. J. Organomet. Chem. 1974, 65, 289301. (b) Strunk, S.;
Schlosser, M. Eur. J. Org. Chem. 2006, 43934397.
4 Sanz, R.; Miguel, D.; Martínez, A.; Pérez, A. J. Org. Chem. 2006, 71, 40244027.
Estudio de la Congelación como Tratamiento previo al Secado Convectivo.
Efecto sobre la Cinética y Calidad de la Remolacha.
F. Vallespir, V. S. Eim, S. Simal, A. Femenia y C. Rosselló
Department of Chemistry, University of the Balearic Islands, Ctra. Valldemossa km 7.5, 07122, Palma de
Mallorca, Spain
[email protected]
La congelación es un tratamiento previo muy utilizado para mejorar el proceso de
transferencia de materia durante el secado que puede afectar, en el caso del secado de
alimentos, a la calidad del producto final1. El objetivo del presente trabajo es evaluar el efecto
de las condiciones de congelación como tratamiento previo al secado, sobre la cinética, y las
características de color y microestructura de remolacha (var. Beta vulgaris) deshidratada. Para
el estudio se seleccionaron muestras con el mismo grado de madurez (7±1 ºBrix),
acondicionadas a geometría cúbica de 0.01 m de arista. Las muestras fueron sometidas a
pretratamientos de congelación en las siguientes condiciones: congelación por convección
(pretratamiento F1: -20 ºC, 1.23 ºC/min y pretratamiento F2: 80 ºC, 2.42 ºC/min) y
congelación por inmersión en nitrógeno líquido (pretratamiento F3: -196 ºC, 272.9 ºC/min).
Posteriormente, las muestras congeladas y la muestra fresca (Control) se procesaron en un
secadero convectivo a escala de laboratorio (50 ºC y 1 m/s) hasta alcanzar un contenido en
humedad de 0.53±0.01 kg agua/kg ss. Al final del proceso de secado se determinó el cambio
total de color2(ΔE2=Δ 2+Δa2+Δb2) en coordenadas CIELab y se observó la microestructura
mediante microscopía electrónica de barrido (SEM).
El tiempo de secado para la muestra Control fue de 2.97 h. Los tratamientos de congelación
redujeron el tiempo de secado un 25.9% (F1), 18.7% (F2) y 2.6% (F3). Por otra parte, el
cambio total de color (ΔE), fue menor en las muestras del tratamiento F3 que en las muestras
de los tratamientos F1 y F2, las cuales presentaron valores mayores y similares entre sí dando
lugar a un mayor oscurecimiento de las muestras respecto al Control. El análisis de la
microestructura (Fig. 1) muestra que el tratamiento de congelación afectó en mayor medida a
las muestras F2 y F3 apareciendo fracturas, disrupciones y mayor compactación de las
paredes celulares que las muestras del tratamiento F1 que fue el menos agresivo.
a
b
c
d
Figura 1. Micrografías SEM. Muestras a) Control b) F1 c) F2 d) F3
Los autores agradecen la financiación (AGL 2012-34627 y DPI2012-37466-C03-02) al
Gobierno Español (MICINN), al Fondo Europeo de Desarrollo Regional (FEDER) y al
Govern de les Illes Balears (57/2011). También agradecen la beca de investigación (BES2013-064131) al Gobierno de España (Ministerio de Economía y Competitividad).
________________________________________________
1. Nemzer, B. Pietrzkowski, Z. Spórna, A. Stalica, P. Thresher, W. Michałowski, T. Wybraniec, S. Food
Chemistry 2011, 127 (1), 42-53.
2. Figiel, A. Journal of Food Engineering 2010, 98 (4), 461-470.
Bilbao, 4-7 Noviembre 2014
Synthesis of New Class of Foldamers Constituted by Densely Substituted
Pyrrolidine Units. Preliminary Organocatalytic Properties.
Maddalen Agirre, Andrea Ruiz-Olalla, Mª de Gracia Retamosa and Fernando P. Cossío*
Departamento de Química Orgánica I, Universidad del País Vasco/Euskal Herriko Unibertsitatea (UPV/EHU)
and Donostia International Physics Center (DIPC), Pº Manuel de Lardizabal 3, 20018 San Sebastián-Donostia,
Spain
[email protected]
Foldamers are described as unnatural oligomers that fold into a conformationally ordered
state in solution.1 Most well-known foldamers are based on β-peptides.2 However, scarce
examples of γ-foldamers had been reported3 due to the low stability of their secondary
structure. We have reported that the (3+2) cycloadditions provide densely substituted
unnatural L- and D-proline derivatives in a stereocontrolled manner.4 Their substitution
pattern gives the opportunity to orthogonally synthesize different γ-proline oligopeptides with
four chiral centers per ring. Encouraged by the good results obtained in aldol reactions by our
pyrrolidine based organocatalysts,4,5 we studied the influence of each building block in this
reaction. The stereochemistry was found to be directly dependent on the behaviour of each
catalytic unit in a nearly additive manner.
Scheme 1
Financial support by the Ministerio de Economia y Competitividad (MINECO) of Spain
(project CTQ2010-16959) and from the Basque Government (Grupos Consolidados IT67313) is acknowledged.
________________________________________________
1 Apella, D. H.; Christianson, L. A.; Karle, I. L.; Powell, D. R.; Gellman, S. H. J. Am. Chem. Soc., 1996, 118,
13071-13072.
2 Cheng, R. P.; Gellman, S. H.; DeGrado, W. F. Chem. Rev., 2001, 101, 3219-3232.
3 (a) Seebach, D.; Brenner, M.; Rueping, M.; Jaun, B. Chem. Eur. J., 2002, 8, 573-584. (b) Seebach, D.;
Schaeffer, L.; Brenner, M.; Hoyer, D. Angew. Chem. Int. Ed. 2003, 42, 776-778.
4 Conde, E.; Bello, D.; de Cózar, A.; Sánchez, M.; Vázquez, M. A.; Cossío, F. P. Chem. Sci. 2012, 3,
1486-1491.
5 Retamosa, M. G.; de Cózar, A.; Sánchez, M.; Miranda, J. I.; Sansano, J. M.; Castelló, L. M.; Nájera, C.;
Jiménez, A. I.; Sayago, F. J.; Cativiela, C.; Cossío, F.P. Submitted.
Caracterización IR de Dímeros de ROH
Pedro F. Arnaiz, Iker León, Raúl Montero, Jorge González, Imanol Usabiaga, Marta
Fernández-Fernández, Virginia Ovejas, Asier Longarte y José A. Fernández
Departamento de Química-Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU),
Bº Sarriena S/N, 48940 Leioa.
[email protected]
La interacción entre alcoholes alifáticos es el ejemplo más sencillo de formación de enlaces
de hidrógeno entre moléculas alifáticas, y por tanto su caracterización precisa es un paso
necesario en el entendimiento de las interacciones intermoleculares entre moléculas orgánicas.
En el presente trabajo, se aborda el estudio de la formación de dímeros entre alcoholes
alifáticos simples, mediante espectroscopía infrarroja con resolución de masas en expansiones
supersónicas.
as distintas especies (monómero, dímero, trímero, tetr mero,…) se generan mediante el
sembrado del vapor del ROH en una expansión supersónica de un gas noble dentro de un
espectrómetro de masas en tiempo de vuelo (TOF). La ionización no resonante mediante un
pulso láser de 800nmy duración de fs permite el estudio de especies sin cromóforo que de otro
modo no son detectables mediante la técnica REMPI. El espectro infrarrojo se obtiene
mediante un segundo láser de IRns, por despoblamiento de la señal de ionización, según la
técnica IRns/IRfs800.1 De este modo, se obtiene el espectro en la región de las bandas de tensión
de los OH.
Para la interpretación de los resultados experimentales se realizó una búsqueda conformacional por mecánica molecular, para posteriormente optimizar las geometrías obtenidas
tanto de los monómeros como de los dímeros por cálculos ab initio. La comparativa del IR
experimental y teórica nos permite determinar la estructura de los confórmeros generados.
[CH3(CH2)5OH]2
[CH3(CH2)4OH]2
[CH3(CH2)3OH]2
[CH3(CH2)2OH]2
[CH3CH2OH]2
[CH3OH]2
3300
3400
3500
3600
3700
3800
Energía/cm-1
Gráfico 1: espectros IR experimentales de [1-alcoholes]2
1 I. León, R. Montero, F. Castaño, A. Longarte y J.A. Fernández, J. Phys. Chem. A, 2012, 116, 6798-6803.
Bilbao, 4-7 Noviembre 2014
Selective Linear Aliphatic Amino Acid Recognition by Fluorescein Derivate
Almudena Martí, Ana M. Costero, Pablo Gaviña and Margarita Parra
Instituto de Reconocimiento Molecular y Desarrollo Tecnológico. Centro mixto Universitat Politécnica de
València-Universidad de València.Departament de Química Orgànica, Universitat de València, Dr. Moliner,50,
46100 Burjassot (Valencia)
[email protected]
The simultaneous binding of cationic and anionic guest species by heteroditopic receptors is a
rapidly developing new field of coordination chemistry. Ion-pair receptors can be used ti
mimic important biological functions and coordinate biologically significant species such as
zwitterionic amino acids and peptides.1
Among the different salts studied, a-amino acids in their zwitterionic form are the most
preferred targets due to their relevance in the biological world. However, less attention has
been devoted to study linear aliphatic amino acids even though they also play important
biological roles. Thus, 4-aminobutyric acid (GABA) is an important neurotransmitter, 5aminopentanoic acid is a metabolic product of cadaverine, and 6-aminohexanoic acid presents
fibrinolytic properties. Amino acids in their zwitterionic form are practically insoluble in
common organic solvents and it is necessary to use derivatized compounds to carry out
organic reactions in non-aqueous media. For this reason, in the course of our studies in
carboxylate recognition and sensing we have focused in designing heteroditopic ligands for
selective linear aliphatic amino acid (ω-amino acid) recognition.2
We report here the synthesis and recognition properties towards the zwitterionic species of
fluorescein derivate.
Scheme 1: Schematic illustration of zwitterinic amino acid and fluorescein derivate.
Acknowledgements: The authors thank the Spanish Government (grant numbers MAT200914564-C04-03 and MAT2012-38429-C04-02) for support. A. M. is grateful to the Spanish
Government for a fellowship.
1 Webber P. R. A. and. Beer P. D; Dalton Trans. , 2003, 2249–2252.
2 Costero A. M., Rodríguez-Muñiz G. M., Gil S., Peransi S., Gaviña P., Tetrahedron , 2008, 64110-116
Synthesis of Novel Dibenzylic Boronic Esters through 1,6-Boron
Conjugate Addition to para-Quinone Methides
Carlos Jarava-Barrera, Alejandro Parra and Mariola Tortosa
Departamento de Química Orgánica, Universidad Autónoma de Madrid, av/ Francisco Tomás y Valiente 7,
Madrid, España
[email protected]
para-Quinone methides (p-QMs),1, which are structurally characterized by the unique
assembly of carbonyl and olefinic moieties, have been already known for more than one
century in organic chemistry.2 In nature, the p-QM unit exists in a variety of natural products
such as fungal metabolites, terpenes, and plant pigments. As a result of the intrinsic
electrophilic reactivity of p-QMs, highly reactive transient p-QM species generated in situ are
implicated in many chemical, medicinal, and biological processes such as lignin biosynthesis,
enzyme inhibition, and DNA alkylation and cross-linking. However, p-QMs have been
scarcely used as starting materials in asymmetric catalysis.3
Recently, our group has been focused on the design of new copper-catalyzed borylation
reactions. In this context, we thought that p-QMs could be suitable electrophiles for an
unprecedented copper-catalyzed 1,6-boron conjugate addition (Scheme 1). Herein, we
describe how Cu(I) complexes can smoothly catalyze the borylation of p-QMs to afford
dibenzylic boronates that can be easily transformed into dibenzylic alcohols.
Scheme 1: 1,6-boron Conjugate Addition of para-Quinone Methides
Acknowledgements: we thank the European Research Council (ERC-DAUBOR-337776) for
financial support.
1 For reviews on the chemistry of p-QMs, see: (a) Turner A. B.; Q. Rev. Chem. Soc. 1964, 18, 347. (b)
“Quinone Methides”: Wagner, H.-U. ; Gompper, R.; in The Chemistry of the Quinonoid Compounds, Vol. 2
(Ed.: S. Patai), Wiley, New York, 1974, chap. 18, 1145.
2 Baeyer, A. ; Villiger, V. ; Ber. Dtsch. Chem. Ges. 1903, 36, 2792.
3 Fan, C. et al, Angew. Chem. Int. Ed. 2013, 52, 9229.
4 (a) Alfaro, R.; Parra, A; Alemán, J.; García Ruano, J. L.; Tortosa, M.; J. Am. Chem. Soc. 2012, 134, 15165.
(b) Tortosa, M; Angew. Chem. Int. Ed. 2011, 50, 3950.
Bilbao, 4-7 Noviembre 2014
Luminescence Properties of Novel Heteroleptic Molybdenum Trinuclear
Clusters Containing Imidazo-phenanthroline Ligands
David Recatalà, Rosa Llusar, Francisco Galindo, Konstantin A. Brylev, Artem L. Gushchin
Departament de Química Física i Analítica, Universitat Jaume I, Av. Sos Baynat s/n, 12071 Castelló, Spain
[email protected]
Transition metal cluster chalcogenides can be conveniently functionalized with different
ligands in order to obtain molecular materials with a number of properties and applications.1
The appropriate choice of outer ligands in M3(µ3-Q)(µ-Q2)3 units (M = Mo, W; Q = S, Se) has
resulted in homoleptic molybdenum or tungsten clusters exhibiting interesting physical
properties. Some examples of them include non-linear optics2 or magnetic conductity.3 In
contrast, the number of heteroleptic complexes is rather scarce mainly due to the difficulty
involved in their synthesis. The coordination of two or more different ligands usually affords
mixtures of complexes which are very difficult to separate by using the traditional purification
techniques.
In this contribution our interest has been focused on the preparation of heteroleptic diimine
complexes starting from [Mo3S7X6]2- units (X = Cl, Br), and most importantly on the
coordination of a novel emissive imidazo[4,5-f]-1,10-phenanthroline ligand with long alkoxy
chains. The species prepared by coordination of this imidazo-phenanthroline ligand represent
to the best of our knowledge, the first examples of trinuclear molybdenum cluster
chalcogenides that exhibit luminescence properties.
7
Fluorescence Intensity (a.u.)
7x10
Ligand in CH2Cl2
1 in CH2Cl2
7
6x10
2 in CH2Cl2
7
5x10
7
4x10
7
3x10
7
2x10
7
1x10
0
350
400
450
500
550
Wavelength (nm)
Figura 1.
1 Rossmeisl, J.; Dahl, S.; Nørskov, J. K.; Chorkendorff, I. et al., Nat. Mater. 2011, 10, 434–438.
2 Garriga, J. M.; Llusar, R.; Uriel, S.; Vicent, C.; Usher, A. J.; Lucas, N. T.; Humphrey, M. G.; Samoc, M.
Dalt. Trans. 2003, 4546.
3 Llusar, R.; Vicent, C. Coord. Chem. Rev. 2010, 254, 1534–1548.
2-Aminobenzimidazole Organocatalyzed Asymmetric Amination of Cyclic
1,3-Dicarbonyl Compounds
Paz Trillo, Melania Gómez-Martínez, Diego A. Alonso* and Alejandro Baeza*
Departamento de Química Orgánica and Instituto de Síntesis Orgánica (ISO), Facultad de Ciencias,
Universidad de Alicante, Apdo 99, 03080 Alicante, Spain
[email protected]
The construction of chiral quaternary stereocentres bearing an amine moiety represents an
important reaction in synthetic organic chemistry due to the importance of compounds
possessing such structure.1 The asymmetric electrophilic amination of prochiral carbonyl
compounds employing diazocarboxylates as nitrogen source is a simple and straightforward
method, particularly the catalytic asymmetric α-amination of prochiral 1,3-dicarbonyl
compounds, since the highly functionalized resulting structures can be further transformed
and elaborated.2,3
In the last years our research group has been interested in the use of transcyclohexanediamine-benzimidazole derivatives as hydrogen bonding organocatalyst in
different organic transformations.4 Therefore, we decided to explore the performance of these
catalysts in the electrophilic amination of 1,3-dicarbonyl compounds. In this way, following
an exhaustive study, we found that benzimidazole II provided the best results obtaining high
yields and enantioselectivities varying form moderate to excellent using smooth reaction
conditions and as low as 1 mol% of catalyst loading. The results of this study are here
presented.5
Scheme 1
1 Christoffers, J.; Mann, A. Angew. Chem. Int. Ed. 2001, 40, 4591.
2 Ciganek, E. In Organic Reactions, Vol 72; Denmark, S. E., Ed.; Wiley:New Jersey, 2008, 1-366.
3 For selected reviews about electrophilic amination, see: (a) Erdik, E. Tetrahedron 2004, 60, 8747. (c)
Guillena, G.; Ramón, D. J. Tetrahedron: Asymmetry, 2006, 17, 1465. (c) Vallribiera, A.; Sebastian, R. M.;
Shafir, A. Curr. Org. Chem. 2011, 15, 1539. (d) Chauhan, P.; Chimmi, S. S. Tetrahedron: Asymmetry 2013,
24, 343.
4 For recent publications from our research group about the use of chiral benzimidazole derivatives in
organocatalysis, see: (a) Almasi, D.; Alonso, D. A.; Gómez-Bengoa, E.; Nájera, C. J. Org. Chem. 2009, 74,
6163. (b) Gómez-Torres, E.; Alonso, D. A.; Gómez-Bengoa, E.; Nájera, C. Org. Lett. 2011, 13, 6106. (c)
Gómez-Torres, E.; Alonso, D. A.; Gómez-Bengoa, E.; Nájera, C. Eur. J. Org. Chem. 2013, 1434. (d) Trillo,
P.; Baeza, A.; Nájera, C. Synthesis, DOI: 10.1055/s-0034-1378618.
5 Trillo, P.; Gómez-Martínez, M.; Alonso, D. A.; Baeza, A. Manuscript submitted.
Bilbao, 4-7 Noviembre 2014
Acoplamientos Cruzados de Tipo Kumada de Cloruros Bencílicos y
Derivados Vinílogos Catalizados por Ni
Rita Soler-Yanes, Manuel Guisán-Ceinos, Elena Buñuel y Diego J. Cárdenas*
Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Campus de
Cantoblanco, 28049, Madrid, España.
[email protected]
El empleo de Ni como catalizador permite llevar a cabo acoplamientos cruzados alquiloalquilo de manera altamente eficiente permitiendo la compatibilidad con una gran variedad de
grupos funcionales.1 Se ha podido demostrar que este sistema catalítico involucra especies
radicálicas en el transcurso de la reacción.2 El uso de reactivos de Grignard como nucleófilo
en estos procesos resulta ventajoso respecto al de otros organometálicos (Zn, B) ya que se
acorta el número de etapas de síntesis. Además, la preparación de reactivos de Grignard
funcionalizados ha experimentado un importante desarrollo.3
En este trabajo se han desarrollado condiciones para el acoplamiento cruzado entre cloruros
bencílicos y alílicos funcionalizados y reactivos de alquilmagnesio catalizado por Ni. Este
estudio establece unas condiciones de reacción que permiten que el proceso transcurra
rápidamente, evitando los problemas de β-eliminación asociados a los acoplamientos alquiloalquilo4 y logrando la compatibilidad con diversos grupos funcionales en presencia de
TMEDA. Por otro lado, el uso de dialil éter como ligando incrementa la velocidad del
sistema, lo que permite llevar a cabo la reacción a baja temperatura y disminuir la carga
catalítica. Algunas evidencias experimentales sugieren que la reacción transcurre a través de
intermedios radicálicos.
Esquema 1
Agradecimientos:
(AVANCAT).
MICINN
(CTQ2010-15927
y
FPI),
UAM
(FPU-UAM),
CAM
1 (a) Jana, R.; Pathak, T. P.; Sigman, M. S. Chem. Rev. 2011, 40, 4937-4947. (b) Vechorkin, O.; Hu, X.
Angew. Chem. Int. Ed. 2009, 48, 2937-2940.
2 (a) Jones, G. D.; Martin, J. L.; McFarland, C.; Allen, O. R.; Hall, R. E.; Haley, A. D.; Brandon, R. J.;
Konovalova, T.; Desrochers, P. J.; Pulay, P.; Vicic, D. A. J. Am. Chem. Soc. 2006, 128, 13175-13183. (b)
Guisán-Ceinos, M.; Soler-Yanes, R.; Collado-Sanz, D.; Phapale, V. B.; Buñuel, E.; Cárdenas, D. J. Chem.
Eur. J. 2013, 19, 8405-8410.
3 Piller, F. M.; Appukkuttan, P.; Gavryushin, A.; Helm, M.; Knochel, P. Angew. Chem. Int. Ed. 2008, 47,
6802-6806.
4 Cárdenas, D. J. Angew. Chem. Int. Ed. 1999, 38, 3018-3020.
Experimental and DFT Studies on Gold-Catalyzed Additions of
O-Nucleophiles to Alkynes
Jesús Cordón,a Gonzalo Jiménez-Osés,b José M. López de Luzuriaga,a Miguel Monge,a M.
Elena Olmosa and David Pascuala
a
Departamento de Química, Universidad de La Rioja, Logroño, Spain. bDepartment of Chemistry and
Biochemistry, University of California, Los Ángeles, United States
[email protected]
The O-nucleophilic attack to alkynes is a benchmark reaction in homogeneous catalysis
whose interest has been renewed with the incursion of gold compounds. Thus, these catalytic
processes have been traditionally studied using compounds of different metals such as Hg1
and Pd2 but, in recent years, several studies with Au catalysts, both Au(I)3 and Au(III),4 have
been reported. The main reason is that the use of these compounds allows the formation of
C-O bonds in a safe and environmentally friendly way, with high conversions and selectivity.
Therefore, we decided to study, experimentally and theoretically, the behavior of different
Au(I) catalysts such as Au(I)-Phosphine, Au(I)-Ylide, Au(I)-NHC Carbene or Au(III)
catalysts like Au(III)-Dithiocarbamate in two examples of O-nucleophilic attack: the
hydration of phenylacetylene and the synthesis of cyclic acetals.
Scheme 1: reactions studied and catalysts used
In view of the experimental results obtained, we have carried out DFT studies in order to
explain the specific role of each catalyst in both reactions. We have proposed the
corresponding catalytic cycles and we have studied the electrophilicity of the catalysts.
1
2
3
4
Janout, A.; Regen, S. L. J. Org. Chem. 1982, 47, 3331.
Kadota, I.; Lutete, L. M.; Shibuya, A.; Yamamoto, Y. Tetrahedron Lett. 2001, 42, 6207.
Gómez-Su rez, A.; Oonishi, Y.; Meiries, S.; Nolan, S. P. Organometallics 2013, 32, 1106.
Cordón, J.; Jiménez-Osés, G.; López-de-Luzuriaga, J. M.; Monge, M.; Olmos, M. E.; Pascual, D.
Organometallics 2014, 33, 3823.
Bilbao, 4-7 Noviembre 2014
Synthesis and Study of Organic Molecules with a Paramagnetic Response
D. Reta Mañeru,a C. Heras,b I. de P.R. Moreira,a J.M. Bofillb and A. López-Calahorrab
a
Departament de Química Física & Institut de Química Teòrica i Computacional (IQTCUB), bDepartament de
Química Orgànica, Universitat de Barcelona, C/Martí i Franquès 1.
[email protected]
Stable open-shell states in purely organic compounds with and even number of electrons are
rarely found in nature. In this work we present a joint work on the synthesis, characterization
and theoretical analysis of a molecule displaying a stable high-spin state accessible by thermal
energy at room temperature, as depicted in Scheme 1.
In order to explain all the experimental evidence indicating the existence of unpaired
electrons, it is proposed a mechanism through which the triplet state is populated. It consists
of a conformational change along the dihedral angle that concerns the two aromatic rings and
the subsequent stabilization of the unpaired electron by means of resonant forms. This implies
two different conformations for triplet and singlet states. In order to assess the validity of the
model, we perform CASSCF geometry optimization of both triplet and singlet states and then
explore several potential energy profiles connecting them. Finally, we perform MRCI
calculations at the selected geometries to accurately locate the electronic states.
It is found that singlet and triplet geometries are different from each other and that there exists
a region of degeneracy around the triplet geometry between the triplet and singlet states at the
MRCI level.
To sum up, the combined experimental and theoretical evidence allows us to conclude that a
mechanism connecting triplet and singlet states exists. This takes place through the torsion of
an imine bond and its barrier can be overcome by thermal energy at room T
Scheme 1: (a) synthetic route of the molecule. (b) Experimental measurements indicating the
existence of unpaired electrons. c) Theoretical model used to rationalize the observed results
A New Library of Neurokinin 1 Receptor Antagonists: Computational
Guided Synthesis and Biological Activity
Rocío Recio,a Noureddine Khiar,b Feliu Maseras,c Bernard Mouillac,d Eleuterio Alvarez,b
Gabriel Borregoa and Inmaculada Fernándeza
a
Departamento de Quıímica Orgánica y Farmacéutica, Facultad de Farmacia, Universidad de Sevilla, 41012
Sevilla, Spain. bInstituto de Investigaciones Quıímicas, C.S.I.C-Universidad de Sevilla, C/. Américo Vespucio,
49, Isla de la Cartuja, 41092 Sevilla, Spain. cInstitute of Chemical Research of Catalonia (ICIQ), Av. Països
Catalans 16, 43007 Tarragona, Spain and dInstitut de Génomique Fonctionnelle (IGF), CNRS-Université
Montpellier I et II, 141 rue de la Cardonille,34094 Montpellier cedex 05, France.
[email protected]
Substance P (SP) was the first discovered and is the best characterized member of the family
of tachykinins. SP is the specific ligand of the neurokinin-1 (NK-1) receptor, a member of the
family of G protein-coupled receptors (GPCRs), which represents one of the most relevant
target families in small molecule drug design.1 Specifically, as a result of the extensive
involvement of SP in physiopathological processes, NK-1 receptors are currently a
therapeutic target of great relevance. The expected benefits for the NK-1 receptor antagonists
include the treatment of migraine, rheumatoid arthritis, asthma, inflammatory bowel disease,
the regulation of central nervous system disorders such as Parkinson's disease, anxiety or
depression, as well as cancer treatment. Based on the structural requirements of the recently
published NK-1 pharmacophore,2 in this communication, we present part of our ongoing
research directed toward the use of 2-amino-4-H-pyrans3 (Figure 1) as a new family of NK-1
antagonists.
Figure 1
In silico studies on the conformational space of these compounds showed good matching
between non-peptidic antagonist CP-96345-NK1 complex and 2-amino-4-H-pyrans- NK1
interactions (figure 1). Moreover, optimization with “onion method”4 gave a good correlation
between the calculated ligand-receptor interaction energies and the corresponding ligand
activities, experimentally determined as NK-1 binding affinity in IPone test.5 Finally, the
evaluation of the anticancer activity and selectivity of the new antagonists studied in lung
adenocarcinoma by MTT assay confirmed the anticancer properties of these compounds and
their selectivity.
Acknowledgements: financial supports from the "Ministerio Economía y Competitividad"
(grant No. CTQ2010-21755-C02-02 and CTQ-2013-49066-C2-2-R) and the "Junta de
Andalucía" (grant No. P11-FQM-8046)
1 Klabunde, T.; Hessler, G. ChemBioChem 2002, 3, 928-944.
2 Evers, A.; Klebe, G. J. Med. Chem. 2004, 47, 5381-5392.
3 Marco, J.L.; Fernández, I.; Khiar, N.; Fernández, P.; Romero, A. J. Org. Chem. 1995; 60, 6678.
4 Maseras, F. and K., M. J. Comp. Chem. 16, 1170.
5 http://www.htrf.com/products/gpcr/ipone/
Bilbao, 4-7 Noviembre 2014
Conformational Preferences of Hybrid /-Peptides Modulated by Cation Interactions
Nuria Mazo, Iván García-González, Francisco Corzana, Jesús H. Busto, Alberto Avenoza,
Jesús M. Peregrina
Departamento de Química, Universidad de La Rioja, Centro de Investigación en Síntesis Química, C/ Madre de
Dios, 51, 26006 Logroño, La Rioja, Spain, phone: +34 941 299630
[email protected]
The incorporation of -amino acids into peptides has been reported to provide a high degree
of enzymatic stability,1 due to the stabilization of unusual secondary structures. The
combination of proteinogenic -amino acid residues and synthetic -amino acids, namely
hybrid /-peptides, further broaden the chemical space of accessible structures with potential
applications. There are only few examples in which a chiral 2,2 amino acid2 is included in
this type of hybrid peptides. In this context, the incorporation of pyridinium salts as side chain
of the peptide could modulate the conformation through different interactions.
In this work, we present the synthesis of several hybrid peptides by the incorporation of 2,2amino acids in different peptides through ring opening of cyclic sulfamidates with pyridine.
Experimental and theoretical studies show the existence of cation/ interactions in compound
3. Theses interactions have attracted considerable interests in the recent years, since these they
are important tools for controlling crystal packing, structures of biological molecules and
molecular recognition processes.3
Scheme 1
________________________________________________
1 K. Mohle, R. Gunther, M. Thormann, N. Sewald and H. J. Hofmann, Biopolymers 1999, 50, 167.
2 J. M. Oaksmith, U. Peters, B. Ganem, B. J. Am. Chem. Soc. 2004, 126, 13606.
3 J. L. Asensio, A. Ardá, F. J. Cañada and J. Jiménez-Barbero, Acc. Chem. Res. 2013, 46, 946.
Nanocatálisis en Síntesis Orgánica: Nueva Preparación de Dihidrofuranos a
Partir de Alenos
Ana María González,a Benito Alcaide,a Pedro Almendros,b Amparo Lunaa
a
Grupo de Lactamas y Heterociclos Bioactivos, Departamento de Química Orgánica I, Unidad Asociada al
CSIC, Facultad de Química, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid,
España. bInstituto de Química Orgánica General, IQOG-CSIC, Juan de la Cierva 3, 28006 Madrid, España
[email protected]
Los alenos son intermedios muy versátiles en Síntesis Orgánica y su reactividad ha centrado
la atención de un gran número de químicos sintéticos, lo que se ha traducido en un elevado
número de publicaciones.1 En particular, la reacción de ciclación de alenos que contienen un
centro nucleófilo en su estructura se ha llevado a cabo por tratamiento con una amplia
variedad de agentes así como de metales de transición, dando lugar a anillos de diferentes
tamaños, con buen control de la regio- y la estereoselectividad.2 Por otro parte, el desarrollo de
procesos químicos con un impacto ambiental mínimo, el uso de agua como disolvente y el
diseño de catalizadores reciclables, es un área de gran interés en la comunidad científica.
Entre los catalizadores compatibles con medios acuosos, las nanopartículas metálicas (NPs)
han atraído la atención de los investigadores en los últimos años.3 Así, en el presente trabajo se
describe un estudio de la reactividad de diferentes α-alenoles sustituidos en presencia de un
sistema catalítico versátil basado en NPs metálicas de Pd(0), lo cual ha permitido la síntesis
selectiva de los productos de oxiciclación con muy buenos rendimientos.
Esquema 1
Agradecimientos: MINECO (Proyectos CTQ2012-33664-C02-01, CTQ2012-33664-C02-02).
1 (a) Yu, S.; Ma, S. Angew. Chem. Int. Ed. 2012, 51, 3074. (b) Krause, N.; Winter, C. Chem. Rev. 2011, 111,
1994. (c) Alcaide, B.; Almendros, P. Adv. Synth. Catal. 2011, 353, 2561. (d) Alcaide, B.; Almendros, P.;
Aragoncillo, C. Chem. Soc. Rev. 2010, 39, 783.
2 (a) Alcaide, B.; Almendros, P.; Quirós, M. T.; Matínez del Campo, T.; Soriano, E.; Marco-Contelles, J. L.
Chem. Eur. J. 2013, 19, 14233. (b) Alcaide, B.; Almendros, P.; Cembellín, S.; Martínez del Campo, T.;
Fernández, I. Chem. Commun. 2013, 49, 1282. (c) Alcaide, B.; Almendros, P.; Alonso, J. M.; Fernández, I.
Chem. Commun. 2012, 48, 6604.
3 (a) Deraedt, C.; Astruc, D. Acc. Chem. Res. 2014, 47, 494. (b) Favier, I.; Madec, D.; Teuma, E.; Gómez, M.
Curr. Org. Chem. 2011, 15, 3127.
Bilbao, 4-7 Noviembre 2014
Interruptores Moleculares Utilizados como Dispositivos de
Almacenamiento de Energía Solar
David Martínez-López, Marina Blanco-Lomas, Diego Sampedro, Pedro J. Campos
Departamento de Química, Centro de Investigación en Síntesis Química, Universidad de La Rioja, C/ Madre de
Dios 51, 26006, Logroño, España.
[email protected]
Una de las aplicaciones más relevantes de los interruptores moleculares es su capacidad de
afectar a sistemas complejos una vez que se han incorporado a ellos.1 Por otra parte, estos
dispositivos también pueden llevar a cabo otros tipos de procesos distintos, donde la
importancia no radica en el cambio geométrico, sino en la energética del proceso de
fotoisomerización.
Se han estudiado las propiedades fotofísicas de distintos interruptores moleculares basados en
la PSB-retinal, (Figura 1) así como el proceso de isomerización E/Z que se produce al irradiar
una disolución del compuesto en una lámpara de Hg de media presión, y la reversión térmica
de dicho proceso. Estos compuestos presentan una banda de absorción en la región del
ultravioleta y la reversión térmica se produce rápidamente a temperatura ambiente.
Figura 1: interruptor molecular basado en la PSB-retinal
En esta comunicación se presentarán los resultados obtenidos tras sintetizar, compuestos que
puedan ser utilizados como celdas de almacenamiento de energía solar (MOST), a partir de
interruptores moleculares previamente estudiados.2 Para ello, se realiza la cuaternización del
nitrógeno imínico con el fin de desplazar la banda de absorción hacia el visible, y aumentar la
barrera energética del proceso térmico Z/E para así poder almacenar los fotones absorbidos
por el isómero E.3
Agradecimientos: Ministerio de Ciencia e Innovación por su aporte económico (CTQ 201124800).
1 M. Blanco-Lomas, S. Samanta, P. J. Campos, G. A. Woolley, D. Sampedro J. Am. Chem. Soc. 2012, 134,
6960.
2 M. Blanco-Lomas, P. J. Campos, D. Sampedro Eur. J. Org. Chem., 2012, 6328.
3 M. Blanco-Lomas, D. Martínez-López, P. J. Campos, D. Sampedro Tet. Lett., 2014, 55, 3361.
Chromo-Fluorogenic BODIPY-complexes for Selective Detection of V-type
Nerve Agent Surrogate
Andrea Barba-Bon, Ana M. Costero, Salvador Gil, Félix Sancenón and Ramón MatínezMáñez
Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Unidad mixta Universidad Politécnica
de Valencia-Universidad de Valencia, Dr. Moliner 50, 46100 Burjassot, Valencia, Spain
[email protected]
The organophosphorous nerve agents, comprised of the G- and V-series agents, are highly
toxic chemical warfare agents (CWAs) that cause incapacitation and death through inhibition
of acetylcholinesterase1. There has been a recent resurgence of interest in exploiting
molecularly based chemical sensing approaches for the detection of CWAs.2 However the
exploitation of non-covalent interactions to drive the association is scarcely reported.3
Investigations into V-type nerve agent surrogate with BODIPY-complexes (Eu3+ and Au3)
were carried out using Uv-Vis. and fluorescence spectroscopy. Addition of V-type surrogate
induced a red-shift in the absorption spectra and a remarkable quenching of the emission
band. A color modulation from bright pink to blue is easily detectable to the naked-eye. We
propose a displacement mechanism in which the V-surrogate acts as a bidentate ligand to the
metallic cation. LOD in the 9-14 ppm range were determined.
Blue
Pink
Scheme 1: Chemical structures of V-type agent and their surrogate; and schematic outline of
the sensing paradigm.
Financial support from the Spanish Government (Project MAT2012-38429-C04) and the
Generalitat Valenciana (Project PROMETEOII/2014/047) is gratefully acknowledged. A.B.B
acknowledges the award of a pre-doctoral FPI fellowship. SCIE (Universidad de Valencia) is
gratefully acknowledged for all the equipment employed.
1 S.M. Somani, Chemical Warfare Agent, Academic Press, San Diego, 1992.
2 (a) K. Kim, O.G. Tsay, D.A. Atwood and D.G. Churchill, Chem. Rev., 2011, 111, 5345-5403. (b) M.R,
Sambrook and S. Notam, Chem. Soc. Rev., 2013, 42, 9251-9267.
3 G.H. Dennison, M.R. Sambrook and M.R. Johnston, Chem.Commun., 2014, 50, 195-197.
Bilbao, 4-7 Noviembre 2014
Compounds of Hybrid Structure Pyridazinone/Coumarin as Potential
Antiplatelet Agents
María C. Costas-Lago,a Pedro Besada,a Ernesto Cano,b Carmen Terána
a
Department of Organic Chemistry, Faculty of Chemistry, University of Vigo, 36310, Vigo, Spain. bDpto of
Pharmacology, Faculty of Pharmacy, Univ. of Santiago de Compostela, 15782, Santiago de Compostela, Spain
[email protected]
Pyridazinone derivatives show important pharmacological properties, and they have
contributed significantly to the development of drugs acting on the cardiovascular system.
The presence of an aryl group in C6 and the absence of substitution in N2 are common
structural features of pyridazinone analogues with antiplatelet, vasorelaxant or cardiotonic
properties1. However, in recent years we have developed series of compounds in which the
aryl group at C6 was replaced by an alkyl chain of varying magnitude functionalized with
alcohol or ether groups, and we have demonstrated that the substitution in N2 is useful for
their antiplatelet activity2. In addition, coumarins are a large family of compounds of natural
and synthetic origin that also show interesting cardiovascular properties, including antiplatelet
activity3.
Bearing in mind the similar cardiovascular effects of both moieties, we have designed and
synthesized pyridazinone derivatives substituted in C6 with coumarin fragments (compounds
4). The new compounds of hybrid structure pyridazinone/coumarin are bioisosteres of the 6aryl pyridazinones and were proposed with the aim of improving the platelet antiaggregatory
activity of the classical analogues.
Scheme 1: a) R1NHNH2, Et3N, EtOH; b) salicyladehyde, piperidine, isopropanol
The compounds 4 were synthesized following the multi-step strategy shown in Scheme 1 and
based on Perkin reaction of pyridazinone intermediates 3 with the appropriate
o-hydroxybenzaldehyde. The key intermediates 3 were obtained in four steps starting from
maleic anhydride, which via a sequence of Diels-Alder, Wittig and retro Diels-Alder reactions
gave the ethyl (5-oxofuran-2-ylidene)acetate 24, a suitable synthon for pyridazinones 3. The
target compounds 4 will be evaluated as antiplatelet agents and the results of this biological
study will be reported.
1 (a) A. Coelho, E. Sotelo, N. Yañez, R. Laguna, E. Raviña, Bioorg. Med. Chem. Lett. 2004, 321-324. (b) A.
Siddiqui, R. Mishra, M. Shaharyar, Eur. J. Med. Chem. 2010, 2283-2290. (c) E. Nashaat-Amin, A.A.M.,
Abdel-Alim, S.G., Adbel-Moty, A.N.A., El-Shorbagi, M. Sh., Abdel-Rahman, Arch. Pharmacol. Res., 2010,
25-46.
2 T. Costas, P. Besada., A. Piras, L. Acevedo, M. Yáñez, F. Orallo, R. Laguna, C. Terán, Bioorg. Med. Chem.
Lett., 2010, 6624-6627.
3 (a) S. Vilar, E. Quezada, L. Santana, E. Uriarte, M. Yáñez, N. Fraiz, C. Alcaide, E. Cano, F. Orallo, Bioorg.
Med. Chem. Lett, 2006, 257-261. (b) E. Quezada, G. Delogu, C. Picciau, L. Santana, G. Podda, F. Borges, V.
García-Morales, D. Viña, F. Orallo, Molecules, 2010, 270-279.
4 (a) Y. Tachibana, M. Yamahata, K. Kasuya, Green Chem., 2013, 1318-1325. (b) R.A. Massy-Westropp, M.F.
Price, Aust. J. Chem., 1980; 333-341.
Síntesis asimétrica de 1,2-Diaminas mediante Cicloadicciones 1,3-dipolares
entre Iluros de Azometino no Estabilizados y N-terc-Butilsulfinilcetiminas
Cristina Izquierdo, José Luís García Ruano, José Alemán y Alberto Fraile
Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco
[email protected]
Las 1,2-diaminas son compuestos de gran importancia que están presentes en productos
naturales de gran interés biológico y en estructuras de compuestos con gran valor sintético en
el campo de la medicina nuclear de diagnóstico. Además, éstas dienaminas cada vez están
siendo más utilizadas como precursores de nuevos azamacrociclos y compuestos
heterocíclicos, los cuáles son empleados como ligandos y auxiliaries quirales 1 en síntesis
asimétrica. Por otra parte; a pesar de que en la bibliografía están descritos un gran número de
ejemplos relativos a las reacciones de azometin iluros estabilizados con una gran variedad de
dipolarófilos, los antecedents relativos al uso de azometin iluros no estabilizados son muy
escasos.
Basados en nuestra experiencia en cicloadicciones 1,3-dipolares2 y en la utilización de Nsulfiniliminas3, nos planteamos llevar a cabo la síntesis diastereoselectiva de compuestos 1,2diamínicos por reacción entre iluros de azometino no estabilizados generados in situ a partir
de N-(metoximetil)-N-(trimetilsililmetil)bencilamina y N-sulfinilcetiminas quirales. En esta
comunicación presentamos la optimización y el alcance de dicha reacción, así como la
derivatización de los correspondientes aductos a las 1,2-diaminas libres.
Esquema 1
.
1 (a) Lucet, D.;Gall, T. L.; Mioskowski, C. Angew. Chem., Int. Ed. 1998, 37, 2580. (b) Bennani, Y.; Hanessian,
S. Chem. Rev. 1997, 97, 3161 y sus referencias citadas.
2 (a) J. Alemán, A. Fraile, M. Leyre, J. L. García Ruano, C. Izquierdo, S. D-.Tendero, Adv. Synth. Catal. 2012,
9, 1665. (b) J. L. García Ruano, A. Tito, M. T. Peromingo, J. Org. Chem. 2002, 67, 981.
3 (a) José L. García Ruano, José Alemán, y José F. Soriano. Org. Lett., 2003, 5 , 677. (b) José L. García Ruano
y José Alemán. Org. Lett.,2003, 5, 4513.
Bilbao, 4-7 Noviembre 2014
High Resolution Lipid Distribution in Human Colon Using MALDI-IMS
Jone Garate,a Roberto Fernández,a Joan Bestard-Escalas,b Daniel Lopez,b Rebeca Reigada,b
Sam Khorrami,b Daniel Ginard,b Gwendolyn Barceló-Coblijnb and José A. Fernándeza*
a
Dep. Of Physical Chemistry, University of the Basque Country (UPV/EHU), Spain. bResearch Unit, Hospital
Universitari Son Espases IdISPa, Palma, Spain
[email protected]
Lipids play an important rol at cellular and whole organism level and therefore there might be
some alteration in different aspect of lipid metabolism that can affect numerous cellular
processes causing diseases such as cancer.
Mass spectrometry has gained momentum on lipidomics with Imagining Mass Spectrometry
due to its ability to obtain the spatial distribution of lipids in tissue sections.
The standard spatial resolution of MALDI-IMS is around 20-100 µm, depending on the
instrument. It is important to achieve better resolution to understand the processes of different
pathologies. Even though there are some new sophisticated optical systems that allow
decreasing the dimensions of the spot of the desorption laser, this can also be achieved by
oversampling the laser beam. The key of this method is the complete ablation of the matrix on
the first shot. That is why the sample preparation parameters and the tune of the experiment
need to be optimized.
Here we show lipid distribution of a human colon biopsies at cellular level (10-5 mm) using
the oversampling technique with an originally elliptical laser beam of 168x37 µm without
losing signal intensity, both in positive and negative ion modes. The increased resolution
allows identifying the lipid distribution of structures that were undistinguishable at resolutions
above 25 mm.
7
1.2x10
7
1.0x10
6
8.0x10
6
m/z: 857.5137
6.0x10
6
4.0x10
6
2.0x10
0.0
5 um
25µm
10µm
5µm
10 um
25 um
600
700
800
900
1000
m/z
Figure 1
Further research will focus on the analysis of these lipid distributions on different biopsies to
get to the understanding of their role in colon cancer.
Síntesis y Caracterización de Membranas Poliméricas Obtenidas por
Electro Estirado de poli-p-clorometilestireno y Líquidos Iónicos Poliméricos
Silvia Montolio, María Isabel Burguete, Eduardo García-Verdugo y Santiago V. Luis
Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, Avda. Sos Baynat s/n E-12071,
Castellón, España
[email protected]
La contaminación debida a derrames de petróleo y aceites ocasionados por accidentes
industriales es una de las causas que origina serios problemas medioambientales. Para
minimizarlos, los investigadores están desarrollando diversidad de materiales absorbentes que
ayuden a su limpieza. Entre sus principales características se incluyen la alta hidrofobicidad,
la resistencia al agua y la reutilización.1,2
En esta comunicación se presentan nuestros esfuerzos en el diseño, caracterización y
aplicación de membranas poliméricas formadas por nanofibras obtenidas por electro estirado
(electrospinning). La simplicidad y versatilidad de este método permite la formación de fibras
de tamaño nanométrico a partir de disoluciones poliméricas.3,4
Las propiedades hidrofóbicas/hidrofílicas de las membranas obtenidas se pueden controlar
variando la naturaleza de los polímeros empleados. Así, el empleo de polímeros lineales de
poli-p-clorometilestireno y sus análogos modificados con unidades de líquidos iónicos nos
permiten obtener membranas poliméricas con propiedades físicas y mecánicas que los hacen
ideales para su aplicación en procesos de filtración y separación.
Figura 1. Esquema del proceso de electrospinning para la obtención de membranas
poliméricas y la demostración su carácter hidrofóbico
Agradecimientos: Ministerio de Ciencia e Innovación (MICINN-CTQ 2011-28903-C02_01 y
FPU12/00667), Generalitat Valenciana (GV-PROMETEO 2012/020) y UJI-P1-1B2013-37
1
2
3
4
Lee, M.W.; An, S.; Latthe, S.S.; Lee, C.; Hong, S.; Yoon, S.S. ACS Appl. Mater. Interfaces 2013, 10597
Wu, J.; Wang, N.; Wang, L.; Dong, H.; Zhao, Y.; Jiang, L. ACS Appl. Mater. Interfaces 2012, 4, 3207
Huang, Z.M.; Zhang, Y.Z.; Kotaki, M.; Ramakrishna, S. Compos. Sci. Technol. 2003, 63, 2223
Pai, C.; Boyce, M.C.; Rutledge, G.C. Macromolecules, 2009, 42, 2102
Bilbao, 4-7 Noviembre 2014
Síntesis de 4-Aminoacilcumarinas Mediante Reacciones de Ugi
Teresa G. Castellano, Ana G. Neo y Carlos F. Marcos
Laboratorio de Química Orgánica y Bioorgánica, Universidad de Extremadura. 10071 Cáceres, Spain
[email protected]
La reacción de Ugi de cuatro componentes (U4CC)1 consiste en la condensación entre una
amina, un oxocompuesto, un isonitrilo y un ácido carboxílico y ha resultado ser una estrategia
muy útil para sintetizar, en tan sólo un paso de reacción, compuestos que poseen una gran
diversidad estructural. Son conocidas variaciones de esta reacción en las que se sustituye la
amina o el ácido carboxílico2 por otros reactivos análogos que cumplan esa función. Esto
permite ampliar la diversidad de esta reacción aunque el número de estructuras obtenibles no
es muy amplio. Recientemente, hemos desarrollado una nueva variante de la reacción
utilizando enoles como componente ácido, en la que se obtiene una gran diversidad
estructural.3
Las cumarinas son compuestos naturales que poseen numerosas aplicaciones en ciencia y
tecnología,4 demostrando tener una amplia variedad de actividades biológicas como
antitumorales5 o antimicrobianas6 entre muchas otras7.
En este trabajo se presenta la utilización de 4-hidroxicumarinas como componente ácido en
reacciones de enol-Ugi. Se ha estudiado la influencia de distintos sustituyentes atractores de
electrones en posición α al enol, así como el uso de distintos disolventes org nicos y acuosos.
Esquema 1: reacción enol-Ugi con derivados de 4-hidroxicumarina
Agradecimientos: Junta de Extremadura and Universidad de Extremadura, Junta de
Extremadura y FEDER.
1 Ugi, I.; Steinbrückner, C., Angew. Chem. 1960, 72, 267.
2 (a) Dömling, A.; Ugi, I., Angew. Chem. Int. Ed. 2000, 3168. (b) El Kaim, L.; Grimaud, L., Tetrahedron 2009,
65, 2153.
3 Castellano, T. G.; Neo, A. G.; Marcaccini, S.; Marcos, C. F., Org. Lett. 2012, 14, 6218.
4 (a) Lafitte, D.; Lamour, V.; Tsvetkov, P. O.; Makarov, A. A.; Klich, M.; Deprez, P.; Moras, D.; Briand, C.;
Gilli, R., Biochemistry 2002, 41, 7217. (b) Lake, B. G., Food Chem. Toxicol. 1999, 37, 423.
5 Dong, Y.; Nakagawa-Goto, K.; Lai, C.-Y.; Morris-Natschke, S. L.; Bastow, K. F.; Lee, K.-H., Bioorg. Med.
Chem. Lett. 2010, 20, 4085.
6 Dekić, B. R. Radulović, N. S. Dekić, V. S. Vukićević, R. D. Palić, R. M., Molecules 2010, 15, 2246.
7 (a) Suresh, M.; Das, A., Tetrahedron Lett. 2009, 50, 5808. (b) Zhu, P. J.; Hobson, J. P.; Southall, N.; Qiu, C.;
Thomas, C. J.; Lu, J.; Inglese, J.; Zheng, W.; Leppla, S. H.; Bugge, T. H.; Austin, C. P.; Liu, S., Biorg. Med.
Chem. 2009, 17, 5139.
Reversible Photo-control of an Antigenic Peptide Conformation
Iris A. Bermejo, David Martínez-López, Jesús H. Busto, A. Avenoza, Jesús M. Peregrina,
Francisco Corzana, Diego Sampedro
Depto. de Química, Universidad de La Rioja, Centro de Investigación en Síntesis Química, 26006 Logroño,
Spain
[email protected]
MUC1 mucin is an O-glycoprotein that is being widely studied as a potential cancer vaccine.1
Its importance lies in the fact that in tumor cells, these proteins are overexpressed and their
carbohydrates are simple due to incomplete glycosylation. Consequently, different tumorassociated carbohydrate antigens are exposed to the immune system. Pro-Asp-Thr(α-OGalNAc)-Arg-Pro determinant, which is included in MUC1 sequence, is the epitope
recognized by most of anti-MUC1 antibodies.
This fragment displays a fixed conformation to satisfy the complementary shape with the
antibody. To study the influence of this conformation on the recognition process and to
module the antigen-antibody binding, we have synthesized the molecule shown in Figure 1. In
this molecule, the epitope recognized by antibodies is linked to a molecular switch based on
E/Z photoisomerization.2 Our preliminary computational studies indicate that this switch has a
significant conformational change after irradiation, so it can drive functional change when
binding to antibodies. The biological evaluation of the two possible states is going to be
evaluated by both ELISA tests and SPR experiments.
Figure 1
1 Gaidzik, N.; Westerlind, U.; Kunz, H. Chem. Soc. Rev. 2013, 42, 4421.
2 Blanco-Lomas, M.; Samanta, S.; Campos, P.J.; Woolley, G.A.; Sampedro, D. J. Am. Chem. Soc. 2012, 134,
6960.
Bilbao, 4-7 Noviembre 2014
The Conformational Landscape of the Anesthetic Enflurane
Cristóbal Pérez,b Elena Caballero-Mancebo,b Montserrat Vallejo-López,b Alberto Lesarri,b
Emilio J. Cocinero,c Jens-Uwe Grabow,d Richard D. Suenram,a Brooks H. Patea
a
Department of Chemistry, University of Virginia, McCormick Rd., Charlottesville, VA 22904-4319 (USA).
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid,
Paseo de Belén, 7, 47011, Valladolid (Spain). cDepartamento de Química Física, Facultad de Ciencia y
Tecnología, Universidad del País Vasco, Apartado 644, 48080 Bilbao (Spain). dInstitut für Physikalische
Chemie und Elektrochemie, Leibniz Universität Hannover, Callinstrabe 3A, 30167 Hannover (Germany)
b
[email protected]
The structural properties of the general anesthetic enflurane have been analysed by a
combination of microwave (MW) spectroscopy and ab initio calculations. The rotational
spectrum was recorded with a broadband (2-18 GHz) chirped-pulsed FT-MW spectrometer
developed at the University of Virginia. Enflurane is a volatile liquid and was expanded in a
supersonic expansion from a diluted gas mixture. The theoretical methods included different
ab initio and DFT methods, which explored the PES of the molecule. Three different
conformations were detected in the spectrum, sharing a trans arrangement of the carbon
skeleton. The internal rotation of the chlorofluoromethyl group generates the observed
conformations. Accurate rotational and nuclear quadrupole coupling parameters were
determined for the parent and different 13C and 37Cl isotopologues. The molecular structure
was determined for the most stable conformer using substitution (rs) and effective (r0)
methods.
Figure 1
Efficiency comparison between different membrane contactors and
[emim][ac] ionic liquid in CO2 absorption
Lucia Gomez-Coma, Aurora Garea, and Angel Irabien
Department of Chemical and Biomolecular Engineering, Universidad de Cantabria. Avda. Los Castros s/n
Santander 39005 SPAIN
[email protected]
Carbon dioxide is one of the major contributors to climate change. The CO2 capture and
sequestration (CCS) is a concern globally today to reduce the impact on the atmosphere and
protect humans against the risks associated with CO2 pollution. Post-combustion process
based on ionic liquids and a membrane contactor have emerged as new attractive alternative
to traditionally systems because of their zero emission solvent features compared to amines
and their controlled interfacial area and independent control of gas and liquid flow rates
respectively.1,2
The aim of the present work is to compare the temperature effect on the efficiency in CO2
absorption using polypropylene and polysulfone commercially available hollow fibre
membrane contactors and two laboratory-made based on PVDF. The 1-Ethyl-3methylimidazolium acetate ([emim][Ac]) was used as solvent. Its high CO2 solubility
converts the process into a promising alternative to common amine processes.
The temperature ranges from 291 to 343K. The IL flows through the shell side and the gas
flows counter-currently on the inside of the hollow fibres. The gas stream has a typical
composition of post-combustion processes including CO2 (15%) and N2 (75%).
Figure 1: experimental set-up
The Spanish Ministry Economy and Competitiveness (Project ENE2010-14828) and the
Royal Spanish Society of Chemistry in Cantabria (RSEQ ST-Cantabria) have funded this
research.
1 Gomez-Coma, L.; Garea, A.; Irabien, A. Sep. Purif. Technol. 2014, 132, 120–125.
2 Luis, P.; Gerven, T.V.; Bruggen, B.V. Prog. Energ. Combust. 2012, 38, 419-448.
Bilbao, 4-7 Noviembre 2014
Reacción Dominó en la Síntesis Asimétrica de Híbridos β-Lactámicos
Nucleósidos
Mateo M. Salgado, Carlos T. Nieto, David Díez y Narciso M. Garrido
Dpto. De Química Orgánica, Universidad de Salamanca, Avda. De Los Caídos s/n 37008 Salamanca
[email protected]
La síntesis de nuevas entidades químicas a través de la fusión de dos restos biológicamente
relevantes ha surgido como una nueva estrategia en los programas de descubrimiento de
fármacos.1 Los motivos para la implementación son la búsqueda de nuevas entidades activas
capaces de eludir la resistencia a fármacos o la explotación de los mecanismos de transporte
activo. Además, los sistemas híbridos permiten el diseño de nuevas estructuras orgánicas a
través de la modificación selectiva de una de las dos entidades, lo cual, puede proporcionar
acceso a los compuestos diana funcionalizados con interés biológico.
D’hooghe y colaboradores2 desarrollaron una nueva clase de sistemas híbridos a través de Nalquilación de 6-benzilamino o 6-bencil-oxipurina con (ω-haloalquilo)-β-lactamas, seguido
por apertura reductora del anillo β-lactama para proporcionar híbridos purina-aminopropanol
los cuales son accesibles desde nuestra metodología.3
Esquema 1.
Recientemente, nuestro grupo de trabajo ha comunicado estrategias de la reacción dominó:
que incluye los reordenamientos de acetato alílico y estereoselectivo de Ireland-Claisen
seguidos de una adición asimétrica de Michael.4 Esta metodología nos permite obtener los δaminoácidos 3 directamente por tratamiento de aductos de Baylis-Hillman 2 con el amiduro
de litio quiral (R)-1.1
1 Decker, M. Current Medicinal Chemistry 2011, 18 (10), 1464-1475.
2 D’hooghe, M. Mollet, K. De Vreese, R. Jonckers, T. H. M. Dams, G. De Kimpe, N. Journal of Medicinal
Chemistry 2012, 55 (11), 5637-5641.
3 Garrido, N. M.; Rosa Sánchez, M.; Díez, D.; Sanz, F.; Urones, J. G.. Tetrahedron: Asymmetry 2011, 22 (8),
872-880.
4 Garrido, N. M.; García, M.; Díez, D.; Sánchez, M. R.; Sanz, F.; Urones, J. G.,. Organic Letters 2008, 10 (9),
1687-1690.
Using Multivariable Analysis over Membrane Microarrays MALDI-IMS
Data for Tissue Classification.
Roberto Fernández,a Tarson Tolentino-Cortez,b Sergio Lage,c Jone Garate,a Egoitz
Astigarraga,b Gabriel Barreda-Gómezb and José A. Fernándeza
a
Department of Physical Chemistry, The University of Basque Country (UPV/EHU), Barrio Sarriena s/n, Leioa
48940, Spain. bIMG Pharma Biotech, Vivero Científico, mod.7 - Ed. Rectorado UPV/EHU, Bº Sarriena s/n,
Leioa 48940, Spain. cMetabolism Unit, Department of Paediatrics, Cruces University Hospital, Plaza de Cruces
s/n, 48903, Barakaldo, Vizcaya, Spain.
[email protected]
Looking for a new methodology, which be useful for tissue classification, in this work
combined MALDI-IMS and Membrane microarrays. Multivariable analysis is an essential
tool in order to get useful information from mass spectrometry data. Principal components
analysis (PCA) and RankCompete analysis have shown as interesting algorithms for data
classification.
10 male Sprague Dawley rats (250-275 g) were used for tissue extraction. Lipid homogenates
were deposited onto standard glass slides using a robot (SpotBot®3 microarrayer, Arrayit).
The arrays were covered with a suitable matrix (2-mercaptobenzothiazole for positive
detection and 1,5-diaminonaphtalene for negative ion mode) using a sublimator. The arrays
were scanned using an LTQ-orbitrap XL (Thermo Scientific) working at 100.000 mass
resolution and 150 µm of spatial resolution. Data handling and analysis was carried out using
MassAnalyst (www.Noraybio.com) and MatLabTM.
We shown here the PCA and RankCompete analysis of the lipid fingerprint of 41 different
kinds of rat tissues obtained in the same experiment using MALDI-IMS over one microarray
printed with all tissue membranes.
Figure 1
Bilbao, 4-7 Noviembre 2014
Materiales de Cobre como Catalizadores Heterogeneos en la Oxidación
Selectiva de Alcohol Bencílico
Yolanda Pérez, Paula Cruz, Isabel del Hierro y Mariano Fajardo
Departamento Biología y Geología, Física y Química Inorgánica. E.S.C.E.T, Universidad Rey Juan Carlos,
28933, Móstoles (Madrid) Spain
[email protected]
El presente trabajo pretende ser una aportación a los procesos de oxidación selectiva de
alcohol bencílico a benzaldehído, compuesto relevante en procesos industriales por sus
importantes aplicaciones en la industria farmacéutica, alimentaria y de perfumería. El
principal inconveniente de este tipo de oxidaciones es que el producto requerido se oxida más
fácilmente que el sustrato inicial, por lo que es difícil obtener una buena selectividad del
proceso. Industrialmente la forma tradicional de obtención de benzaldehído es la hidrólisis de
cloruro de bencilideno. En este proceso el benzaldehído formado contiene trazas de cloro
haciéndolo inservible para su empleo en productos farmacéuticos. Esto, sumado al hecho de
que el proceso genera gran cantidad de residuos contaminantes desemboca en la necesidad de
nuevas rutas sintéticas.
Por ello, nos planteamos diseñar catalizadores heterogéneos selectivos hacia el producto de
interés, y encontrar un proceso lo más limpio posible donde el benzaldehído quede libre de
cloro y pueda ser posteriormente empleado. El empleo de catalizadores heterogéneos presenta
novedosas ventajas ya que permiten la fácil separación del catalizador del medio de reacción
y con ello su utilización en sucesivas reacciones. Además el empleo de nanopartículas supone
un incremento considerable del área superficial por unidad de volumen gracias a su pequeño
tamaño (<100 nm) lo cual constituye un aspecto fundamental en la catálisis heterogénea.
Se han diseñado nuevos materiales de cobre, en concreto, nanopartículas de cobre soportadas
sobre sílice mesoestructurada, SBA-15. En primer lugar, el cobre se incorporó al soporte
utilizando varios métodos grafting (G), post-grafting (PG) e impregnación a volumen de poro
(IMP). En una segunda etapa se obtienen nanopartículas de Cu por reducción con hidracina.
El estudio demuestra que el método de síntesis del material es fundamental para obtener
catalizadores heterogéneos con buena actividad y selectividad para la reacción de oxidación
de alcohol bencílico a benzaldehído, utilizando H2O2 como oxidante y agua como disolvente.
Los resultados más significativos muestran que los materiales compuestos de nanopartículas
de cobre presentaron mejor selectividad.
Me
HN
NH2
H2N
Me
Si
NH
HN
+
Me
O
Si Me
Si
Cu(NO3)23H2O
O
EtO
Me Me
Si
EtO
OH
OEt
O
OEt
O
Cu-PDA-HMDS-SBA-15
SiMe 3
SiMe 3
PDA
OH
N
OH
+
N
N
SBA-15
+
N
ClO
Si
O
EtO
EtO
OH
Si
ClCuCl2
Cu-IL-SBA-15
OEt
OH
OEt
IL
Esquema 1: preparación de materiales de Cu
Highly Enantioselective Copper (I)-Catalyzed Conjugate Addition of
1,3-Diynes to α,β-Unsaturated Trifluoromethyl Ketones
Amparo Sanz-Marco, Gonzalo Blay* and José R. Pedro*
Departament de Química Orgànica, Universitat de València, 46100-Burjassot, Spain
[email protected]
The asymmetric conjugate addition of terminal alkynes to enones is a highly efficient method
to obtain compounds with internal alkynes bearing a stereogenic center at propargylic
position. There are several catalytic systems for the asymmetric addition of terminal alkynes
to enones,1 however a protocol for the analogous transformation with terminal 1,3-diynes has
not been reported so far.
On the other hand, the enantioselective addition of terminal 1,3-diynes to prochiral carbonyl
and imine substrates has been described. In all cases, the addition has been carried out by
using zinc acetylides and different catalysts or chiral auxiliaries. Thus, in 2010, Trost and coworkers developed the enantioselective addition of 1,3-diynes to aldehydes using a dinuclear
zinc ProPhenol system.2 In 2011, Ma performed an enantioselective 1,2-addition of 1,3diynes to aromatic ketones in presence of Copper(II)-hydroxycamphor-sulfonamide complex
and Me2Zn.3 Later in 2012, the same author described the enantioselective addition of 1,3diynes to N-sulfonyl aldimines4 and acyclic α-CF3 ketimine esters5 by using Me2Zn and chiral
binol-type ligands.
In this communication, we describe the first asymmetric conjugate addition of terminal 1,3diynes 2 to α,β-unsaturated trifluoromethyl ketones 1, using a copper(I)-biphenylphosphane
complex as catalyst, to give the β-1,3-diynyl trifluoromethyl ketones 3 with good yields and
excellent enantioselectivities. These compounds are interesting building blocks on account of
the versatile chemistry of the diyne and the ketone moieties.
Scheme 1
Financial support from the Ministerio de Ciencia e Innovación and FEDER (CTQ200913083) and from Generalitat Valenciana (ACOMP/2012/212 and ISIC/2012/001) is
acknowledged. A S-M thanks the MICINN for a pre-doctoral grant (FPI)..
1
(a) Wu, T. R.; Chong J. M. J. Am. Chem. Soc. 2005, 127, 3244. (b) Yazaki, R.; Kumagai, N.; Shibasaki, M.
2
3
4
5
J. Am. Chem. Soc. 2010, 132, 10275. (c) Blay, G.; Cardona, L.; Pedro, J. R.; Sanz-Marco, A. Chem. Eur. J.
2012, 18, 12966. (d) Sanz-Marco, A.; García-Ortiz, A.; Blay, G.; Pedro, J. R. Chem. Commun. 2014, 50,
2275.
Trost, B. M.; Chan, V. S.; Yamamoto, D. J. Am. Chem. Soc. 2010, 132, 5186.
Liu, T.-L.; Ma, H.; Zhang, F.-G.; Zheng, Y.; Nie, J.; Ma, J.-A. Chem. Commun. 2011, 47, 12873.
Liu, T.-L.; Zhang, F.-G.; Zheng, Y.; Yao, Q.; Ma, J.-A. Chem. Commun. 2012, 48, 12234.
Zhang, F.-G.; Ma, H.; Zheng, Y.; Ma, J.-A. Tetrahedron 2012, 68, 7663.
Bilbao, 4-7 Noviembre 2014
Enantioselective (3+2) Intramolecular Cycloadditions: Asymmetric
Synthesis of Unnatural Tricyclic Proline Esters
Aitor Lacambra,a,b Ivan Rivilla,a Fernando P. Cossío,a,* Stéphane Quideaub,*
a
Departamento de Química Orgánica I, Universidad del País Vasco – Euskal Herriko Unibertsitatea
(UPV/EHU) and Donostia International Physics Center(DIPC), Pº Manuel Lardizabal 3, 20018, San SebastiánDonostia, Spain. bInstitut Européen de Chimie et Biologie, 2 rue Robert Escarpit, 33607, Pessac, France
[email protected]
Unnatural pyrrolidines are of great interest due to their relevance in synthetic and medicinal
chemistry. In particular, recently has been described that some of these tricyclic compounds
have some activity as TRPV1 agonists as they are capsaicin analogs, which could be of
importance against localized chronic pain.1
Within this context our group has developed a successful strategy for the synthesis of
enantiopure pyrrolidine derivatives using chiral ferrocenyl-proline ligands and transition
metals in (3+2) intermolecular cycloadditions.2
Grigg and coworkers described the first silver mediated intramolecular (3+2) cycloaddition
with stoichiometric amounts of metallic salts.3 Since then, this pathway led to the synthesis of
tricyclic pyrrolidines in its racemic version. In 2005, Pfaltz et al. published a diastereo- and
enantioselective intramolecular reaction using PHOX as chiral assistant and silver as metal
source.4
As an additional contribution in this field, we describe in this communication the use of
ferrocenyl-proline and β-lactam ligands as chiral source combining the use of metals of group
11 (Scheme 1). This combination will lead to the chemical synthesis of polycyclic pyrrolidine
derivatives in an enantio- and diastereoselective manner.
Scheme 1. General (3+2) intramolecular cycloaddition reaction using ferrocenyl-proline
ligands.
1 Painter, T. O.; Kaszas, K.; Gross, J.; Douglas, J. T.; Day, V. W.; Iadarola, M. J.; Santini, C. Bioorg. Med.
Chem. Lett., 2014, 4, 963-968.
2 Conde, E.; Bello, D.; de Cózar, A; Sánchez, M.; Vázquez, M. A.; Cossío, F. P. Chem. Sci. 2012, 3, 14861491.
3 Barr, D. A.; Grigg, R.; Guanaratne, H. Q. N.; Kemp, J.; McMeekin, P.; Shridaran, V. Tetrahedron, 1988, 44
(2), 557-570.
4 Stohler, R.; Wahl, F; Pfaltz, A.; Synthesis, 2005, 9, 1431-1436.
Desarrollo de Membranas Monolíticas Tubulares Mediante Procesos de
Polimerización
Daniel Nuevo, Raúl Porcar, Eduardo García-Verdugo, M. Isabel Burguete, Santiago V. Luis
Departamento de Química Inorgánica y Orgánica, Universidad Jaume I, Campus Del Riu Sec, Av. de Vicent Sos
Baynat, s/n 12071, Castellón, España
[email protected]
En la búsqueda de procesos químicos con bajo impacto medioambiental, la química verde
adquiere día a día una mayor importancia. En este sentido se hace necesario el desarrollo de
metodologías sencillas que permitan la integración de los procesos químicos y en particular
sistemas donde se unifiquen los procesos de reacción y purificación. Las membranas
poliméricas tubulares juegan un papel importante en este campo. Este tipo de membranas son
capaces de separar mezclas bifásicas o emulsionantes y además pueden servir de soporte para
diferentes catalizadores facilitando así la integración de procesos de reacción/separación.
Pump
Pressure sensor
Reactor
Compound 1
Mixture
Pressure regulator
Figure 1
En este trabajo se describe el método de preparación y la caracterización de diversas
membranas polimérica tubulares con utilidad en el campo de la microfiltración. Se trata de
membranas preparadas mediante una mezcla de monómeros estructurales y de
entrecruzamiento en presencia de una sustancia porogénica adecuada para dar lugar a
polímeros macroporosos monolíticos. El empleo de distintas mezclas monoméricas nos
permite controlar, entre otras, variables como la resistencia mecánica, la porosidad y la
formulación química de la superficie polimérica. Así, esta se puede “decorar” con grupos
terminales susceptibles de ser sustituidos por otros. Esta característica es fundamental tanto
para “adaptar” la membrana a una separación específica, modulando su polaridad superficial,
como para poder soportar catalizadores tales como metales o enzimas.1
Agradecimientos: MICINN (CTQ, 2011-28903-C02-01),
(PROMETEO/2012/020) y UJI-P1-1B2013-37.
Generalitat
Valenciana
1 Sans, V.; Karbass, N.; Burguete, M. I.; Compañ, V.; García-Verdugo, E.; Luis, S. V.; Pawlak, M., Chem.
Eur. J. 2011, 17, (6), 1894-1906.
Bilbao, 4-7 Noviembre 2014
Synthesis of a C-glycoside Analog of Tn Antigen
Claudio D. Navo, Carlos Aydillo, Alberto Avenoza, Jesús H. Busto, Francisco Corzana,
María M. Zurbano and Jesús M. Peregrina
Departamento de Química, Universidad de La Rioja, Centro de Investigación en Síntesis Química, C/Madre de
Dios, 51, 26006 Logroño, La Rioja, Spain, phone: +34 941 299630.
[email protected]
Due to the deal of interest for the development of vaccines for cancer treatment,1 several
mimics of Tn antigen (-O-GalNAc-Ser/Thr) have been developed in order to understand the
role of this antigen in disease and to improve their immunogenicity. In this field, we
developed the synthesis of a conformationally restricted mimic of Tn antigen, using as a key
step the asymmetric Michael reaction showed in Scheme 1 and recently reported by our
research group.2 In this work, starting from the Michael adduct, we have carried out the
synthesis of a new C-glycoside analog of Tn antigen.
Scheme 1: synthetic route
This new C-glycoside presents the carbohydrate moiety directly attached to the -carbon of
serine by a C-C bond, instead of being attached to the hydroxyl group. This is an important
fact, considering that the biological activity is tightly related to the structure.
This compound could be used as a building-block in peptide synthesis, coupling other amino
acids to its C-terminal position. It also presents its hydroxyl group protected as O-acetyl,
which could eventually be liberated and glycosylated, having then a very interesting C,Odiglycoside.
1 Heimburg-Molinaroa, J.; Lumb, M.; Vijayc, G.; Jain, M.; Almogrene, A.; Rittenhouse.Olson, K. Vaccine
2011, 29, 8802.
2 Aydillo, C.; Navo, C. D.; Busto, J. H.; Corzana, F.; Zurbano, M. M.; Avenoza, A.; Peregrina, J. M. J. Org.
Chem. 2013, 78, 10968.
Nuevos Derivados de Fullereno[60]: Síntesis de Ciclobutenos
Silvia Reboredo, Rosa M. Girón, Salvatore Filippone y Nazario Martín
Departamento de Química Orgánica I, Facultad de Químicas, Universidad Complutense de Madrid, Av.
Complutense S/N 28040 Madrid. IMDEA–Nanoscience, Campus de Cantoblanco, 28049 Madrid
[email protected]
Desde el descubrimiento de la molécula de fullereno[60] por Robert F. Curl, Sir Harold W.
Kroto y Richard E. Smalley en 1985,1 han sido numerosos los intentos realizados para llevar a
cabo la funcionalización de este interesante alótropo molecular del carbono. Entre las
abundantes reacciones encaminadas a la síntesis de derivados fullerénicos, se encuentran las
fructíferas metodologías de Prato, o Bingel, que han permitido acceder a derivados cíclicos de
cinco y tres eslabones respectivamente. Sin embargo, dada la difícil activación ligada a esta
singular molécula, la construcción de nuevos compuestos cíclicos derivados del C60 puede
considerarse hoy día un interesante reto para los químicos orgánicos.
En los últimos años en nuestro grupo de investigación se han desarrollado diversas
metodologías sintéticas para la formación de compuestos heterocíclicos de cinco eslabones de
manera eficiente. De esta manera, hemos sido pioneros en el empleo de diferentes métodos de
activación organocatalíticos para la preparación de ciclopenteno[4,5:1,2][60]fullerenos y
fulleropirrolinas con excelentes valores de rendimiento y enantioselectividad.2
En este trabajo se ha realizado un estudio detallado que conduce a la formación de
ciclobutenos derivados de fullereno[60] bajo condiciones organocatalíticas. Este sencillo
método es compatible con el empleo tanto de alenoatos como alquinoatos diferentemente
sustituidos (Esquema 1).
Esquema 1: síntesis de derivados de fullereno[60]
Agradecimientos: este trabajo ha sido financiado por European Research Council ERC-2012ADG_20120216 (Chirallcarbon), el Ministerio de Economía y Competitividad (MINECO)
(proyecto CTQ2011-24652), y la CAM (MADRISOLAR-2 proyecto S2009/PPQ-1533).
1 Kroto, H. W.; Heath, J. R.; O´Brien, S. C.; Curl, R. F.; Smalley, R. E. Nature 1985, 318, 162.
2 (a) Marco-Martínez, J.; Marcos, V.; Reboredo, S.; Filippone, S.; Martín, N. Angew. Chem., Int. Ed. 2013, 52,
5115. (b) Marco-Martínez, J.; Marcos, V.; Reboredo, S.; Filippone, S.; Martín, N. J. Am. Chem. Soc. 2014,
136, 2897.
Bilbao, 4-7 Noviembre 2014
Immobilization of Pyrene-Tagged NHC Complexes onto Graphene: an
Efficient Route to Highly Recyclable and Active Catalysts
Sara Sabater, Jose A. Mata and Eduardo Peris
Dept. Química Inorgánica y Orgánica. Universidad Jaume I, Av. Vicente Sos Baynat s/n. Castellón. E-12071
[email protected]
Graphene and derivatives have attracted increasing attention because of their unique physical
and chemical properties and they offer a unique opportunity to non-covalent modifications by
-stacking interactions with molecules containing polycyclic aromatic hydrocarbons1,2.
M = Pd, Ru
Figure 1
In this work, we study the preparation and catalytic properties hybrid catalysts based on Nheterocyclic carbene ligand with a pyrene-tag and reduced graphene-oxide (rGO)
immobilized onto the surface of rGO by -stacking.
The catalytic properties of the molecular complexes and hybrid materials have been studied in
the hydrogenation of alkenes and alcohol oxidation. The results show that the catalytic
properties are improved in the hybrid materials, compared to the catalytic outcomes provided
by the homogenous analogues3.
We thank the financial support from the Ministerio de Ciencia e Innovación of Spain
(CTQ2011-24055/BQU) and Bancaixa (P1.1B2010-02). We would also like to thank the
‘GeneralitatValenciana’ for a fellowship (S. Sabater).
________________________________________________
1. Su, C.; Loh, K. P. Accounts Chem Res 2013, 46, 2275-2285.
2. Mao, X.; Su, H.; Tian, D.; Li, H.; Yang, R. ACS Appl. Mater. Interfaces 2013, 5, 592-597.
3. Sabater, S.; Mata, J. A.; Peris, E. ACS Catal 2014, 4, 2038-2047.
Formación de Enlaces C–NH2 Mediada por Complejos de Iridio
Inmaculada Mena, Miguel A. Casado, Pilar García-Orduña, Víctor Polo y Luis A. Oro
Departamento de Química Inorgánica, ISQCH, Universidad de Zaragoza-CSIC, Zaragoza
[email protected]
El proceso de hidroaminación catalítica de alquenos con amoníaco en condiciones de presión
y temperatura moderadas está considerado como uno de los diez retos de la química actual.1
Para poder alcanzar esta meta es necesario conocer el mecanismo operativo en esta
transformación. La formación de enlaces C–N puede suceder a través de procesos de
inserción migratoria del alqueno en enlaces M–N o mediante un ataque nucleofílico de la
amina (o NH3) a un alqueno coordinado al metal.
En este trabajo se expone la formación estequiométrica de enlaces C–NH2. Esta
transformación tiene lugar a través de dos protocolos sintéticos distintos; sin embargo en
ambos casos es operativo el mismo mecanismo de formación: ataque nucleofílico
intermolecular a una olefina coordinada a iridio.
En el primer caso, el tratamiento del amido complejo trinuclear [{Ir(μ-NH2)(tfb)}3] (tfb =
tetrafluorobenzobarreleno), producto de un proceso de activación de amoníaco,2 con fosfanos
(PR3, R = PMePh2, PMe2Ph, PEt3) da lugar a la formación de complejos mononucleares
[Ir(1,2-2-4--C10H8F4(NH2))(PR3)3], productos de acoplamiento C–NH2 entre un grupo
amido y el carbono vinílico de una diolefina. En el segundo caso, el borboteo de amoníaco y
metildifenilfosfano sobre una disolución de [Ir(Cl)(tfb)(PMePh2)2] da lugar a la obtención del
mismo complejo final.3
Esquema 1
La extensión de esta reactividad para incorporar regioselectivamente un fragmento amino a
una olefina a partir de amoníaco puede representar un avance muy importante en la
hidroaminación de alquenos.
Agradecimientos: Proyecto CTQ2012-356665 y Programa CONSOLIDER INGENIO- 2010.
________________________________________________
1 Haggin, J, Chem. Eng. News 1993, 71, 23.
2 Mena, I., Casado, M.A., García-Orduña, P., Polo, V., Lahoz, F. J., Fazal, A., Oro, L. A. Angew. Chem. Int.
Ed. 2011, 123, 11939.
3 Mena, I., Casado, M.A., Polo, V., García-Orduña, P., Lahoz, F. J., Oro, L. A. Angew. Chem. Int. Ed. 2014,
53, 9627.
Bilbao, 4-7 Noviembre 2014
Estudio teórico y experimental de la primera interacción no soportada
entre centros de Au(I)-Pb(II)
Raquel Echeverría, Jose María López de Luzuriaga, Miguel Monge y M. Elena Olmos
Departamento de Química. Centro de Investigación en Síntesis química (CISQ). Universidad de La Rioja,
Complejo Científico-Tecnológico, 26006, Logroño, Spain.
[email protected]
El estudio de las interacciones metalofílicas entre centros de Au(I) y otros metales de capa
cerrada es un área de investigación en continuo crecimiento debido, especialmente, a las
propiedades fotofísicas asociadas a estas interacciones. En este sentido, uno de los tipos de
interacciones que presentan un gran interés por ser un área poco explorada, es el de las
interacciones entre centros de Au(I) con metales de los grupos 13, 14 y 151.
De hecho, hasta la fecha no se conoce ningún ejemplo de compuestos que presentan una
interacción no soportada entre centros de Au(I) y Pb(II). Únicamente se ha caracterizado
estructuralmente el complejo [Au2Pb(CH2P(S)Ph2)4]2, que presenta una interacción
Au(I)···Pb(II) soportada, y en el que un ligando bidentado actúa como puente entre ambos
metales.
En esta comunicación, se describe la síntesis de compuestos del tipo [HB(pz)3Pb][AuR2] (pz
= pirazolato; R = C6F5- (1), C6Cl2F3- (2), C6Cl5- (3)), en los que se observa, por primera vez, la
presencia de interacciones Au(I)-Pb(II) no soportadas en estado sólido. En los tres casos, se
ha determinado su estructura mediante difracción de Rayos X.
Esquema 1
Además, estos compuestos presentan unas propiedades fotoluminiscentes que pueden ser
sintonizadas en función de los ligandos perhalofenilo unidos a los centros de Au(I).
Por otro lado, se han llevado a cabo cálculos teóricos con el fin de estudiar la naturaleza de la
interacción metalofílica Au(I)-Pb(II) y el origen del comportamiento luminiscente de este tipo
de derivados.
Agradecimientos: MINECO por la financiación del Proyecto (CTQ 2013-48635-C2-2-P).
MINECO por la beca predoctoral FPI a Raquel Echeverría.
1 Modern Supramolecular Gold Chemistry, Gold-Metal Interactions and Applications (Ed.: A. Laguna),
Wiley-VCH, Weinheim, 2008.
2 S. Wang, G. Garzon, C. King, J. C. Wang, J. P. Fackler, Jr., Inorg. Chem. 1989, 28, 4623
One-pot Synthesis of Halo-Heterocycles by Neutral and Selective Reagents.
Aitziber Irastorza,a Franciso J. Fernandez,a Zaira Monasterio,a Nerea Pérez-Esnaola,a Maialen
Sagartzazu-Aizpurua,a Jesús M. Aizpuruaa,*
Departamento de Química Organica-I, Universidad del País Vasco UPV/EHU, Joxe Mari Korta R&D Center.
Avda. Tolosa-72. 20018 San Sebastián. Spain.
[email protected]
Halogenated imidazoles and 1,2,3-triazoles are interesting synthetic intermediates and
suitable components for supramolecular interactions1 and as ionic liquids2. We report the
Ag2O/XCN (X=I,Br) system as an efficient hydrogen/halogen exchange promoter for 1,3imidazolium salts and 1,2,3-triazolium cations3. The operational procedure was very simple
and pure products were obtained in high yields after a single filtration, without the need of
chromatographic purification. The method is applicable to partially functionalized alkyl and
aryl substituted 5-halo-1,2,3-triazolium salts, which are readily available from azides and
alkynes by “click” chemistry.
Scheme 1: C-halogenation of imidazolium salts and triazolium salts by Ag2O/XCN (X=Br,I)
system.
Acknowledgements: we thanks the founding foundations, Gobierno Vasco (ETORTEK: IE
11-304 (nanoIKER-11)). Grants to A. I (PRE_2013_1_447) and Z. M. (UPV/EHU-PIF
10/2010) are acknowledged.
1 Beale, T. M.; Chudzinski, M. G.; Sarwar, G.; Taylor, M. S. Chem. Soc. Rev. 2013, 42, 1667-1680.
2 Khan, S. S.; Shah, J.; Liebscher, J. Tetrahedron. 2010, 66, 5082-5088.
3 Aizpurua, J. M.; Fratila, R. M.; Monasterio, Z.: Peréz-Esnaola, N.: Andreieff, E.; Irastorza, A.; SagartzazuAizpurua, M. New J. Chem. 2014, 38, 474-480.
Bilbao, 4-7 Noviembre 2014
Diseño y Evaluación de un Complejo BODIPY-CuII como Sensor
Fluorogenico para NO
L. Alberto Juárez, Andrea Barba-Bon, Ana M. Costero and Margarita Parra
Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Universitat de València, Dr. Moliner
50, 46100 Burjassot, Valencia, Spain
[email protected]
El óxido de nitrógeno es un gas tóxico cuyos efectos adversos en la salud humana y el medio
ambientes son ampliamente conocidos, por otro lado, el NO regula importantes procesos
biológicos cuyos mecanismos no son bien conocidos. Esto hace que haya un gran interés en el
desarrollo de nuevos sistemas de detección1. El utilizar complejos metálicos como sensores
ópticos tiene entre sus grandes ventajas la reversibilidad del sistema y, por otro lado, la
utilización de un Bodipy como unidad señalizadora hace que se puedan observar cambios
importantes en sus propiedades ópticas ya que poseen altos rendimientos cuánticos en
fluorescencia y gran estabilidad química.
En este trabajo hemos querido usar la conocida capacidad de complejación de bipiridinas con
metales en estado de oxidación (II)2 y se ha sintetizado un Bodipy cuya posición meso está
sustituida con este grupo. Este Bodipy compleja el CuII siendo el complejo Bodipy-CuII no
fluorescente.
Es conocido que el CuII en presencia de NO gas se reduce a CuI,3 el cual no es complejado por
este sistema. Nuestro Bodipy-CuII sintetizado resulta un sistema sensor por desplazamiento
tipo off-on, ya que en ausencia de NO permanece inalterado, mientras que en presencia de NO
el Cu (II) se reduce a Cu(I), la bipiridina no es capaz de complejarlo y se restaura la
fluorescencia del Bodipy, que tiene una longitud de onda de emisión a 520.5nm.
Figura 1: sistema de reconocimiento
En estudios realizados con NO gas se ha observado el incremento de la intensidad de
fluorescencia a la longitud de onda correspondiente al Bodipy libre, siendo el límite de
detección obtenido para NO gas de 3.69 ppm, que se encuentra por debajo de los límites
permitidos, regulados por el Real Decreto 1073/2002 que se bases en la Directiva de la Unión
Europea 1999/30/CE que entró en vigor en el año 2010.
1 M. E. Jun, B. Roy, K. H. Ahn, Chem. Commun. 2011, 47, 7583.
2 W. Wu, J. Sun, X. Cui, J. Zhao, J. Mater. Chem. C. 2013, 1, 4577.
3 M. Sharma, A. Kalita, P. Kumar, A. Singh, B. Mondal, J. Am. Chem. Soc. 2010, 132, 7846.
Experimental and Theoretical Evaluation of DNA-Based Heterobimetallic
Complexes as Catalysts for (3+2) Cycloadditons in Water
Iván Rivilla,a Abel de Cózar,a,b J. Ignacio Santos,c Jose I. Miranda,c Fernando P. Cossíoa,*
a
Departamento de Química Orgánica, Facultad de Química, Universidad del País Vasco-Euskal Herriko
Unibertsitatea (UPV/EHU), Pº Manuel Lardizabal 3, 20018, San Sebastián-Donostia and Donostia
International Physics Center (DIPC) P.O. Box 1072, 20018 San Sebastián-Donostia. bIKERBASQUE, Basque
foundation for Science, 48013 Bilbao. cNMR Facility, SGIKER, Universidad del País Vasco-Euskal Herriko
Unibertsitatea, Pº Manuel Lardizabal 3, 20018, San Sebastián-Donostia
[email protected]
DNA has emerged as a versatile scaffold for synthesis and catalysis being the inspiration for a
new class of bio-organometallic catalysts possessing an organometallic moiety. 1 These
compounds should combine the catalytic activity of transition metals with the well-defined
architecture of DNA, thus increasing, or even improving the amount of currently available
catalysts. In this work we decided to explore the effectiveness of this kind of compounds on
(3+2) cycloaddition reactions between N-metallated azomethine ylides and -deficient
alkenes.2
In an initial set of experiments we studied the coordination
pattern of the platinum atom to DNA selecting guanosine
monophosphate (GMP) as a model ligand. Due to the low
solubility of GMP-Pt(II) complexes, solid NMR experiments
were carried out. These set of experiments verify the coordination
of Pt to the N7 of GMP (fig. 1). Moreover, computational studies
on DNA intrastrand cis-{(2,2’-bipy)Pt(II)d[GpG]} complexes
Figure. 1
within DFT framework were carried out in order to locate and
characterize the energetically feasible possible conformers.
Once the coordination of 2,2’-bipyPt(II)Cl2 to GMP was analyzed, we
synthesized a new hybrid catalyst
based on salmon testes DNA (stDNA) and 2,2’-bipy-Pt(II). The
resulting hybrid system was studied
as catalyst on the (3+2) cycloaddition reactions between azomethine ylides and different
maleimides in water that would give
rise to densely substituted unnatural
prolines (fig. 2).
Figure 2
Formation of endo-cycloaducts was observed in all cases. Furthermore, QM/MM calculations
on the reaction mechanisms unveiled the origins of this stereochemical outcome. .
1 A. J. Boersma, R. P. Megens, B. L. Feringa, G. Roelfes Chem. Soc. Rev., 2010, 39, 2083-2092.
2 A. De Cózar, F. P. Cossío, Phys. Chem. Chem. Phys. 2011, 13, 10858-10868.
Bilbao, 4-7 Noviembre 2014
Synthetic Approach to Tripartin, a Naturally Occurring Histone
Demethylase Inhibitor
Lucía Guillade, Susana Álvarez, Rosana Álvarez,* Ángel R. de Lera*
Organic Chemistry Department. Universidade de Vigo. Vigo. Spain
[email protected]
Histone methylation plays a major role in biology by regulating transcription, maintaining
genomic integrity and contributing to epigenetic effects. The dynamic methylation of lysine
and arginine residues has diverse transcriptional outcomes, with different methylation sites
and states being associated with activation or repression of transcription. The methylation of
specific lysine residues is regulated by the competition of two enzymes, histone
methyltransferases (HMTs) and histone demethylases (KDMs). Several KDMs are targets for
the treatment of diseases such as leukemia, breast, and prostate cancers and inflammation.
Only a few KDM selective inhibitors have been indentified despite their importance in the
regulation of these therapeutic targets. Tripartin, a new dichlorinated indanone, was recently
isolated from the culture broth of the Streptomyces sp. associated with a larva of the dung
beetle Copris tripartitus Waterhouse. This natural product displayed specific activity as an
inhibitor of the histone H3 lysine 9 demethylase KDM4 in HeLa cells.1
Figure 1
For the study of these properties, and the inhibition mechanism of tripartin, we became
interested in an enantioselective and racemic synthesis of the natural product. Using the
indanone structure as starting material, we propose the generation of chirality by using a
Sharpless Asymmetric Dihydroxylation (SAD) followed by the dichloromethyl group
formation using different approaches (1). Other proposal strategy consists in the synthesis of
the indanone structure with phenol groups followed by a nucleophilic addition (1,2) and a
benzylic oxidation (2).
Scheme 1
1 Kim, S.; Kwon, S.; Park, S.; Lee, J.; Bang, H.; Nam, S.; Kwon, H.; Shin, J.; Oh, D. Org. Lett. 2013, 15, 1834.
An Enantioselective Chiral BrØnsted Acid Catalyzed Reaction between
Cyclic Enamines and Hydrazones
Nagore Zabaleta, Uxue Uria, Efraim Reyes, Luisa Carrillo, Jose L. Vicario*
Departamento de Química Orgánica II, Facultad de Ciencia y Tecnología, UPV/EHU, P.O. Box 644, 48080
Bilbao, Spain
[email protected]
In the last decade, chiral phosphoric acids have been widely used to develop several
enantioselective reactions due to their bifunctional character as BrØnsted acids and Lewis
bases.1 One of the most explored activation modes of these catalysts is the protonation of an
electrophile, creating a chiral ion pair which would control the stereochemical outcome of the
reaction.2 In this context, and trying to increase the number of transformations involving
chiral BINOL-phosphates we have developed the enantioselective BrØnsted acid catalyzed
1,2-addition reaction of hydrazones to cyclic enamines.
Scheme 1
This is the first time that a cyclic enamine is activated by a chiral BrØnsted acid catalyst to
generate an N-acyl iminium ion acting as the electrophile of the reaction. The obtained
adducts are synthetically important, constituting a versatile class of compounds due to the
possibility of being derivatized.3
Acknowledgements: Financial support by the Spanish MICINN (CTQ2011-22790 and Juan
de la Cierva Contract to U.U.), the Basque Government (Grupos IT328-10) and UPV/EHU
(EHUA12/09 and UFI QOSYC 11/22 and fellowship to N.Z.) is gratefully acknowledged.
Membership in the COST Action CM0905 is also acknowledged.
1 (a) Parmar, D.; Sugiono, E.; Raja, S.; Rueping, M. Chem. Rev. 2014, 114, 9047. (b) Rueping, M.; Kuenkel,
A.; Atodiresei, I. Chem. Soc. Rev. 2011, 40, 4539. (c) Zamfir, A.; Schenker, S.; Freund, M.; Tsogoeva, B. S.
Org. Biomol. Chem. 2010, 8, 5262.
2 Rueping, M.; Sugiono, E.; Theissmann, T.; Kuenkel, A.; Köckritz, A.; Pews-Davtyan, A.; Nemati, N.; Beller,
M. Org. Lett. 2007, 9, 1065.
3 Job, A.; Janeck, C. F.; Bettray, W.; Peters, R.; Enders, D. Tetrahedron 2002, 58, 2253.
Bilbao, 4-7 Noviembre 2014
Aplicaciones Sintéticas de los Ácidos 2-Quinonil Borónicos
Jaime Rojas-Martín, Marcos Veguillas, María Ribagorda, M. Carmen Carreño
Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, E-28049 Madrid
(España)
[email protected]
Las quinonas conforman un grupo de moléculas de gran interés tanto sintético como
biológico.1 Esta reactividad está muy influenciada por las propiedades electrónicas de los
sustituyentes del sistema quinónico, de forma que la introducción de determinados
sustituyentes puede modular su reactividad, incrementando el inherente potencial de las
quinonas. En nuestro grupo de investigación, se ha sintetizado una nueva familia de ácidos 2quinonil borónicos y se ha estudiado su reactividad en reacciones de Diels-Alder2 y de
alquilación de Friedel-Crafts,3 comprobándose que la presencia del ácido borónico potencia
enormemente su reactividad, y actúa como un controlador temporal de la regioselectividad.
En este trabajo se presenta la síntesis de twistenodionas y de benzoquinonas alquil sustituidas
a partir del ácido 2-quinonil borónico (1). En primer lugar se ha estudiado la reactividad entre
1 y 2-alquenil N-metilindoles, encontrándose que en condiciones suaves de reacción se
obtienen esqueletos de twistenodionas altamente funcionalizadas, con buenos rendimientos y
excelentes regio- y diastereoselectividades. La quinona 1 evoluciona a través de un proceso
dominó que implica una reacción de Friedel-Crafts, una reacción de Diels-Alder
intramolecular (IMDA) y una protodesboronación.4 Así mismo, se ha desarrollado una
metodología de síntesis de benzoquinonas alquil sustituidas, a partir de ácidos 2-quinonil
borónicos y ácidos 1,4-dimetoxiaril borónicos (2), empleando como etapa clave la reacción de
adición conjugada de ácidos borónicos a enonas catalizadas por rodio.5 Este último proceso se
hecho extensivo a la adición a aldehídos aromáticos catalizada por rodio.6
Figura 1
Agradecimientos. Este trabajo ha sido financiado por el Ministerio de Economía y
Competitividad (Proyecto CTQ2011-24783). J. R. agradece la beca FPI concedida por el
MINECO en 2012.
1 (a) S. Patai, Z. Rappaport, The Chemistry of Quinonoid Compounds, Vol II, Wiley: New York, 1988. (b)
Thomson, R. H.; Naturally Occurring Quinones IV. Recent Advances, Blackie: London, 1997.
2 (a) M. C. Redondo, M. Veguillas, M. Ribagorda, M.C. Carreño, Angew. Chem. Int. Ed. 2009, 48, 370. (b) M.
Veguillas, M. C. Redondo, M. Ribagorda, M. C. Carreño, Chem. Eur. J. 2010, 16, 3707.
3 M. Veguillas, M. Ribagorda, M. C. Carreño, Org. Let. 2011, 13, 656.
4 J. Rojas-Martín, M. Veguillas, M. Ribagorda, M. C. Carreño, Org. Let. 2013, 15, 5686.
5 Para reviews sobre formación de enlaces C-C catalizada por Rh, ver: (a) K. Fagnou, M. Lautens, Chem. Rev.
2003, 103, 169. (b) T. Hayashi, K. Yamasaki, Chem. Rev. 2003, 103, 2829
6 M. Saikai, M. Ueda, N. Miyaura, Angew. Chem. Int. Ed. 1998, 37, 3279
Enantioselective Direct Michael Addition of Azlactones and Cyanoacetates
to α’-Oxy Enones
Eider Badiola, Antonia Mielgo, Jesús García, José M. Odriozola, Jesús Razkin, Mikel
Oiarbide and Claudio Palomo*
Departamento de Química Orgánica I, Facultad de Química, Universidad del País Vasco (UPV/EHU), Manuel
Lardizabal 3, 20018 Donostia, Spain
[email protected]
Studies in our group have shown that α’-oxy enones react in the presence of Brønsted base
catalysts with cyanoesters and azlactones to give the corresponding 1,5-dicarbonyl Michael
adducts with a fully substituted carbon center in high enantioselectivity. The Michael addition
of both cyanoesters 3 and azlactones 6 to β-non-substituted enones 1 and 2 is efficiently
promoted by catalyst C1. The reaction has also found to be efficient with β-substituted α’hydroxy enones 9 and cyanoesters.
Besides their utility for the installation of aldehyde and ketone functionality, α’-oxy enones,
through simple oxidative cleavage of the ketol moiety in the resulting adducts, act as α-βunsaturated carboxylic acid surrogates for which successful methodologies are notably
deficient.
Scheme 1
Acknowledgements: UFI QOSYC 11/12, GV IT-291-07, SAIOTEK 2012, MICINN
CTQ2013-47925-C2
Bilbao, 4-7 Noviembre 2014
Molecular Recognition on Nanostructured Surfaces
Nerea Bilbao and David González-Rodríguez*
Nanostructured Molecular Systems and Materials group, Departamento de Química Orgánica, Universidad
Autónoma de Madrid, 28049 Madrid, Spain
[email protected]
This project aims at the development of an innovative methodology based on molecular selfassembly for the nanostructuration of surfaces which are able to selectively recognize
functional -conjugated host molecules. The main objectives are: i) the molecular component
synthesis; ii) the self-assembly process in solution; iii) the formation of nanostructured
monolayers; iv) the molecular recognition on surfaces.
The preparation of the different nucleobase derivatives and molecular building-blocks,
connected via Sonogashira coupling reactions would be explained. The mentioned buildingblocks will allow us to obtain supramolecular functional nanostructures such as rectangular
tetramer macrocycles via selective hydrogen-bonding between the complementary
nucleobases. Self-assembled macrocycle networks will be studied by Scanning Tunneling
Microscopy (STM) on different surfaces.1,2
Scheme 1: self-assembled macrocycle network observed by STM at the solid-liquid interface
octanoic acid/HOPG.
1 Lei, S.; De Feyter S., Nano Lett. 2008, 8, 2541.
2 Ciesielski, A.; Samori, P., Adv. Mater 2010, 22, 3506.
C-Halogenation of Terminal Alkynes by Halocyanogens
Franciso J. Fernandez, Zaira Monasterio, Jesús M. Aizpurua*
Departamento de Química Organica-I, Universidad del País Vasco UPV/EHU, Joxe Mari Korta R&D Center.
Avda. Tolosa-72. 20018 San Sebastián. Spain.
[email protected]
Terminal haloalkynes are both versatile intermediates in organic synthesis and important
building blocks in material science.1 However, there are few commercially available 1iodoalkyenes and new methods enabling their synthesis remain desired. We report the novel
Ag2O/XCN (X = I, Br) system as an efficient hydrogen/halogen exchange promoter for
terminal alkynes. No cyanation side reaction was observed for any instance when
iodocyanogen and bromocyanogen pseudohalogens were used.2 The iodation reaction was
found to be more efficient than the bromation and chemoselective C-halogenations could be
conducted on potentially multifunctional substrates (e. g. 4-alkynyl-1,2,3-triazolium salts).
Scheme 1: C-halogenation of terminal alkynes using the Ag2O/XCN (X=Br,I) system.
Acknowledgements: grants to Z. M. (UPV/EHU-PIF 10/2010) are acknowledged.
1 Liang, L.; Wilhelm, C.; Sun, A.; Grey, C. P.; Lauher, J. W.; Goroff, N. S. J. Am. Chem. Soc. 2008, 130,
7702-7709.
2 Okamoto, M.; Watanabe, M.; Sakata, N.; Murai, M.; Ohe, K. Org. Lett. 2013, 15, 5810-50813.
Bilbao, 4-7 Noviembre 2014
Catalytic Enantioselective Quick Entry to Aldol-Tethered 1,6- and 1,7Enynes and their Synthetic Application
Mikel Oiarbide, Jesús M. García, José M. Odriozola, Jesús Razkin, Irati Lapuerta, Amaiur
Odriozola, Iñaki Urruzuno, Silvia Vera and Claudio Palomo
Dpto. De Química Orgánica I, Facultad de Ciencias Químicas UPV/EHU, Pº Manuel Lardizabal 3, 20018
Donostia-San Sebastian, España
[email protected]
Herein we present an effective asymmetric route to functionalized 1,6- and 1,7- enynes based
on a direct cross-aldol reaction between ω-unsaturated aldehydes and propargylic aldehydes
(α,β-ynals) promoted by combined α,α-dialkylprolinol ether/Brønsted acid catalysis. This
synergistic activation strategy is a key to access the corresponding aldol adducts with high
enantio- and diastereoselectivity.1 The aldol reaction also proceeds well with propargylic
ketones (α,β-ynones) thus enabling a stereocontrolled access to the corresponding tertiary
alcohols. The utility of these adducts, which are difficult to prepare through standard
methodology, is demonstrated by their transformation into trisubstituted bicyclic enones using
standard Pauson-Khand conditions.2
Scheme 1
1. E. Gomez-Bengoa, J. M. García. S. Jimenez, I. Lapuerta, A. Mielgo, J. M. Odriozola, M. Oiarbide, I. Otazo,
I. Urruzuno, S. Vera, C. Palomo. Chem. Sci. 2013, 4, 3198-3204.
2 M. Oiarbide, J. M. García, J. M. Odriozola, J. Razkin, I. Lapuerta, A. Odriozola, I. Urruzuno, S. Vera, C.
Palomo. Chem. Eur. J., 2014, in press.
Synthesis of oligo(phenylene-ethynylenes) glycosides photomodulables
Elisa Deni,a,b Maria Ribagorda,a Anna Barattuccib and Carmen Carreñoa
a
Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Madrid
(España). bDipartimento di Scienze Chimiche, Università degli Studi di Messina, Messina (Italia)
[email protected]
The control of biological systems with light is a major scientific frontier in the areas of
Optogenetics, and Photodynamic Therapy (PDT). The family of oligo(phenyleneethynylenes) (OPEs) represent a peculiar class of luminescent and robust molecular wires.
Their photo-physical properties can be modulated modifying their π-conjugated rigid skeleton
and the substitution of the aromatic system. They have found applications in fluorescentimaging microscopy, which allows the interpretation of biological processes at molecular and
cellular levels and in medical diagnosis.1
Here we present the synthesis of a new family of sugar based OPEs using a Heck-Cassar’s
cross-coupling reaction.2 Our results demonstrated that the modulation of the hydrophobic
chain length and the substituents on the central moieties changed the photophisical properties
and the bioaffinity in cytoplasmic vesicles of HEp-2 cells (cells from epidermoid carcinoma
larynx tissue). Moreover, we have synthetized a new class of soluble sugar oligophenylene
ethynylene (OPE) azobenzenes,3 and study their photocromic properties (cis-trans
isomerization) in the presence of appropriate radiation, with the final scope of building an
hydrosoluble and biocompatible molecular switcher.
Scheme 1
________________________________________________
1 Dascier, D; Ji, E.; Parthasarathy, A.; Schanze, K. S.; Whitten, D.G. Langmuir 2012, 28, 11286
2 Barattucci, A.; Deni, E.; Bonaccorsi, P.; Ceraolo, M. G.; Papalia, T.; Santoro, A.; Sciortino, M. T.;
Puntoriero, F., J. Org. Chem., 2014, 79, 5113-5120
3 Merino, E., Chem. Soc. Rev., 2011, 40, 3835-3853
Bilbao, 4-7 Noviembre 2014
An Experimental and Computational Study of Graphene-Triazolium π-π
Stacking Interactions
Nerea Pérez-Esnaola,a José I. Miranda,b J. Ignacio Santosb and Jesús M. Aizpuruaa
a
Universidad del País Vasco(UPV/EHU). Departamento de Química Orgánica-I and bSGIKER-RMN. Joxe Mari
Korta R&D Center. Avda. Tolosa-72. 20018 San Sebastián.
[email protected]
1,2,3-Triazolium salts are novel ionic liquids1, readily accessible by “click” chemistry, but
their non-covalent interactions with carbonaceous compounds remain largely unexplored.
Herein, we report the first computational study (HF/3-21G*) on the - stacking of 1,3,4trimethyl-1,2,3-triazolium tetrafluoroborate and graphene, as well as an experimental
determination (1H-NMR) of the Ka association constants2 of various triazolium salts (2-3) in
organic solvents using pyrene (Pyr) as a model. These triazolium salts formed π-π stacking
assemblies with graphene and pyrene, whereas analogous triazoles (1) did not, giving 1:1
complexes3. The nature of the solvent, the substituents and the counterion determined the
strength of the interaction. In addition, π-π stacking of triazolium tetrafluoroborate 2b with
graphene was confirmed by 19F-ssNMR. On the other hand, an intramolecular π-π interaction
was observed for pyrene-triazolium derivate 5, but not for analogous triazole 4.
Host
Guest
Assembly
ΔE
(Kcal)*
Graphene
-2.2
Graphene
-21.0
Graphene
-7.2
-3.4
*Calculated in vacuo. (Gaussian09. HF/3-21G*)
1 Schulze, B.; Schubert, U.S. Chem. Soc. Rev., 2014, 43, 2522-2571.
2 Salvatierra, D.; Díez, C.; Jaime, C.J. J. Incl. Phenom. & Molec. Recogn. , 1997, 27, 215-231.
3 (a) Aizpurua, J.M. et al. Synthesis, 2011, 17, 2737-2742. (b) Aizpurua, J.M. et al. New J. Chem., 2014, 38,
474-480.
Métodos Organocatalíticos en Química de Fullerenos
Rosa M. Girón,a Silvia Reboredo,a Juan Marco-Martínez,a Salvatore Filipponea y Nazario
Martína,b,*
a
Departamento de Química Orgánica I, Facultad de Química, Universidad Complutense, E-28040 Madrid,
España. bIMDEA–Nanociencia, Campus de Cantoblanco, E-28049 Madrid, España.
[email protected]
Los fullerenos están ampliamente reconocidos como bloques de construcción moleculares con
interesantes aplicaciones en diferentes campos científicos manteniéndose activas múltiples
líneas de investigación.1 El control de la quiralidad tanto en el ámbito de la biomedicina, así
como en la ciencia de los materiales,2 representa uno de los retos actuales más importantes en
la ciencia de los fullerenos, ya que la morfología de los sólidos y las propiedades de los
materiales pueden verse influenciadas por la presencia de centros estereogénicos.3
En nuestro grupo se ha desarrollado un método que permite, por primera vez, una
funcionalización del fullereno con elevada estereoselectividad mediante el empleo de
metales.4 Más recientemente, basado en la cicloadición (3+2) de alquinoatos con dipolarófilos
coordinantes previamente descrita,5 se ha desarrollado un método organocatalítico usando
fosfinas en la reacción entre el C60 y alenoatos dando lugar a
ciclopenteno[4,5:1,2][60]fullerenos con elevados ee´s.6
En esta comunicación, se mostrarán nuevas metodologías de inducción de quiralidad en el
fullereno mediante organocatalizadores basados en fosfinas, así como la extensión del alcance
de la reacción a nuevos dipolos y dipolarófilos y el estudio del papel de la fosfina en el
mecanismo de reacción.
Esquema 1: síntesis de ciclopenteno[4,5:1,2][60]fullerenos mediante cicloadición (3+2) de
alquinoatos sobre C60.
Agradecimientos: European Research Council ERC-2012-ADG_20120216 (Chirallcarbon),
Ministerio de Economía y Competitividad (MINECO) de España (proyecto CTQ2011-24652;
Consolider-Ingenio CSD2007-00010), Photogenerated Hydrogen by Organic Catalytic
Systems FP7-ENERGY-2012-1-2STAGE nº 309233 (PHOCS) y el CAM (MADRISOLAR-2
proyecto S2009/PPQ-1533). N. M. gracias a la Fundación Alexander von Humboldt.
1 Li, C.; Yip, H.; Jen, A. J. Mater. Chem. 2012, 22, 4161.
2 Wang, Y.; Xu, J.; Wang, Y.; Chen, H. Chem. Soc. Rev. 2013, 42, 2930.
3 Hizume, Y.; Tashiro, K.; Charvet, R.; Yamamoto, Y.; Saeki, A.; Seki, S.; Aida, T. J. Am. Chem. Soc, 2010,
132, 6628.
4 (a) Filippone, S.; Maroto, E. E.; Martín-Domenech, A.; Suarez, M.; Martín, N. Nat. Chem. 2009, 1, 578. (b)
Maroto, E. E.; Filippone, S.; Martín-Domenech, A.; Suarez, M.; Martín, N. J. Am. Chem. Soc. 2012, 134,
12936.
5 Zhang , C.; Lu, X. J. Org. Chem., 1995, 60, 2906.
6 Marco-Martínez, J.; Marcos, V.; Reboredo, S.; Filippone, S.; Martín, N . Angew. Chem. Int. Ed. 2013, 52,
5115.
Bilbao, 4-7 Noviembre 2014
Synthesis and Reactivity of γ-Dipeptides Based on Unnatural Densely
Substituted Pyrrolidines on Enamine-activated Reactions
Andrea Ruiz-Olalla, Mª de Gracia Retamosa, Maddalen Agirre and Fernando P. Cossío*
Departamento de Química Orgánica I, Universidad del País Vasco-Euskal Herriko Unibertsitatea (UPV/EHU)
and Donostia International Physics Center (DIPC), Pº Manuel de Lardizabal 3, 20018 San Sebastián-Donostia,
Spain
[email protected]
By using hybrid ferrocenyl-pyrrolidine ligands (La and Lb) developed in our laboratories, we
are able to synthesize densely substituted 4-nitropyrrolidines in stereodivergent manner
depending on the ligand used.1 The present work shows follow up chemistry on these
pyrrolidines, such as hydrogenation of the nitro moiety or hydrolysis of the ester scaffold and
further peptide coupling. These straightforward transformations provide a large family of γdipeptides based on unnatural proline units. Next, we have studied them in different
enamine-activation based reactions, such as aldol or Michael reaction.2
Scheme 1
Financial support by the Ministerio de Economia y Competitividad (MINECO) of Spain
(project CTQ2010-16959) and from the Basque Government (Grupos Consolidados IT67313) is acknowledged.
1 (a) de Cózar, A.; Cossio, F. P. Phys. Chem. Chem. Phys. 2011, 13, 10858-10868. b) Conde, E.; Bello, D.; de
Cózar, A.; Sánchez, M.; Vazquez, M. A.; Cossío, F. P. Chem. Sci. 2012, 3, 1486-1491. c) Retamosa, M. G.;
de Cózar, A.; Sánchez, M.; Miranda, J. I.; Sansano, J. M.; Castelló, L. M.; Nájera, C.; Jiménez, A. I.; Sayago,
F. J.; Cativiela, C. ; Cossío, F. P. Submitted.
2 Fanelli, R. and Piarulli, U. (2013) Oligopeptides as Modular Organocatalytic Scaffolds, in Comprehensive
Enantioselective Organocatalysis: Catalysts, Reactions, and Applications (ed P. I. Dalko), Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim, Germany.
Desimetrización de Ciclopropenos Catalizada por Cu: Síntesis
Ciclopropilboronatos Quirales
Manuel Guisán Ceinos, Alejandro Parra, Laura Amenós, Aurora López, José Luis García
Ruano y Mariola Tortosa*
Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid
[email protected]
La síntesis de ciclopropilboronatos quirales supone un interesante reto dentro de la química
orgánica que además permite la obtención de derivados de Boro muy versátiles sintéticamente
en procesos de formación de ciclopropenos funcionalizados.1 En la actualidad son pocas las
metodologías que permiten obtener de manera enantioselectiva este tipo de compuestos,
existiendo solo dos ejemplos que emplean la catálisis asimétrica.2 Nuestro grupo de
investigación tiene una contrastada experiencia en reacciones de borilación catalizadas por
Cu3 y, en este sentido, pensamos que esta metodología sería extensible a la síntesis de
ciclopropilboronatos.
En este trabajo se presenta el primer sistema catalítico basado en Cu que permite la obtención
de ciclopropilboronatos quirales, por desimetrización de ciclopropenos, en un proceso
altamente diastereo- y enantioselectivo. Adicionalmente el empleo de aminas secundarias
benzoiladas ha permitido la obtención de los correspondientes derivados de aminoboración
con elevados niveles de diastereoselectividad.
Esquema 1
Agradecimientos: Agradecemos al MINECO (CTQ-2012-35957) y al Consejo Europeo de
Investigacion (ERC Starting Grant 337776-DAUBOR) por la financiación recibida.
1 Liskey, C. W.; Harwtwig, J. F. J. Am. Chem. Soc., 2013, 135, 3375-3378.
2 (a) Zhong, C.; Kunii, S.; Kosaka, Y.; Sawamura, M.; Ito, H. J. Am. Chem. Soc., 2010, 132, 11440-11442. (b)
Rubina, M.; Rubin, M.; Gevorgyan, V. J. Am. Chem. Soc., 2003, 125, 7198-7199.
3 (a) Alfaro, R.; Parra, A.; Alemán J.; García-Ruano, J. L.; Tortosa, M. J. Am. Chem. Soc., 2012, 134, 1516515168. (b) Tortosa, M. Angew. Chem. Int. Ed., 2011, 50, 3950-3953.
Bilbao, 4-7 Noviembre 2014
Synthesis of Highly Labile all-trans-Carotenoids by Bi-directional HornerWadsworth-Emmons Condensation
Marta Castiñeira Reis, Belén Vaz Araujo, Rosana Àlvarez Rodriguez, Ángel Rodriguez de
Lera
Organic Chemistry, University of Vigo, Campus As Lagoas Marcosende. 36310, Vigo, Spain
[email protected]
The evolution of the human race has been accompanied by the tireless struggle against natural
selection, towards survival. Although the essence of this little fight prevails, the weapons used
have changed and improved radically: sticks and stones have turned nowadays into drugs and
technology. Nevertheless this ancient fight not just to survive but to improve live quality is far
from being overcome, and is here were science and particularly Organic Synthesis must play
a critical role. In this crusade, polyenic compounds can behave as critical fighters due to their
antioxidant activity. Among the diverse functions of carotenoids in Nature, their role in
photosynthesis and photoprotection is the most important for the producing organisms and
also for those that should ingest them, as is evidenced by their function in some diseases as
cataracts and Alzehimer among others.
As an extension of the studies of our research group towards the total synthesis of
carotenoids, the double HWE condensation of a central polyene with two terminal units
appropriately functionalized has been recently explored for the preparation of highly labile
carotenoids,1 due to its stereoselectivity and functional group compatibility. Thus the two
carotenoids octadehydro-β,β-carotene,2 and auroxanthin2,3 have been turned as interesting
targets, not just for their intrinsic instability but also for their structural complexity. Parallel,
these targets open the chance to study a stereoselective synthesis of the lateral fragments.
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1. (a) Otero, L.; Vaz, B.; Alvarez, R.; de Lera, A. R., Total synthesis of (8R,6'R)-peridinin-5,8-furanoxide.
Chem. Commun. (Cambridge, U. K.) 2013, 49, 5043-5045. (b) Fontan, N.; Dominguez, M.; Alvarez, R.; de
Lera, A. R., Synthesis of C40-Symmetrical Fully-Conjugated Carotenoids by Olefin Metathesis. Eur. J. Org.
Chem. 2011, 2011, 6704-6712, S6704/1-S6704/20.
2. Fiksdahl, A.; Liaaen-Jensen, S., Algal caroteneoids. Part 38. Diacetylenic caroteneoids from Euglena viridis.
Phytochemistry 1988, 27, 1447-50.
3. Allen, M. B.; Goodwin, T. W.; Phagplongarm, S., Carotenoid distribution in certain naturally occurring algae
and in some artificially induced mutants of Chlorella pyrenoidosa. J. Gen. Microbiol. 1960, 23, 93-103.
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