October 19-22, 2015
Angra dos Reis – RJ, Brazil
BOOK OF ABSTRACTS
Brazil-France Bilateral Workshop
“Organometallic Catalysis for Green and Sustainable Chemistry”
19 - 22 October 2015
Angra dos Reis – RJ, Brazil
Joint with the 5th Latin American Symposium on Coordination and Organometallic
Chemistry, (SILQCOM), this workshop aims at bringing together chemists from Brazil and
France with complementary, strong and diverse expertise in one of the pillars supporting
green chemistry: homogeneous catalysis for clean processes leading to complex
molecules and materials, biomass transformations into useful industrial intermediates,
biodegradable polymers, and energy economy or generation.
Brazil Coordinators
France Coordinators
Prof. Dalmo Mandelli
Centro de Ciências Naturais e Humanas
Universidade Federal do ABC
[email protected]
Prof. Pierre H. Dixneuf
Institut des Sciences Chimiques
University of Rennes-CNRS
[email protected]
Prof. Eduardo N. dos Santos
Department of Chemistry - ICEx
Federal University of Minas Gerais
[email protected]
Dr. Christian Bruneau
Institut des Sciences Chimiques
University of Rennes-CNRS
[email protected]
Green Chemistry focuses on the design and implementation of chemical technologies,
processes and services that are safe, energy efficient and environmentally sustainable.
Adopting Green Chemistry innovations gives industry sustainable product and process
alternatives that will continue to meet market demands while enhancing sustainability,
improving human health and driving the economy, thereby advancing the human
condition. Sustainable chemistry is a scientific concept that seeks to improve the
efficiency with which natural resources are used to meet human needs for chemical
products and services. Catalysis is not only the main pillar of the 12 principles of green
and sustainable chemistry but it also contributes to most of these principles such as atom
economy and no waste reactions, no toxic intermediates and products, safe solvents
including water, energy generation and efficiency, renewable feedstocks as raw
materials. Catalysis takes the best profit of these principles for the building of complex
molecules and natural products, medicinal drugs, molecular materials and polymers or
key industrial intermediates, via clean and low energy processes.
Several challenges in catalysis for green and sustainable chemistry will be addressed
during the bilateral seminar seeking for strong cooperations and faster innovations in the
future for the profit of both countries.
1. C-H bond functionalization and cross-coupling reactions
2. Alkene metathesis catalysis adding value to natural products
3. Catalysis and energy
4. Catalytic biomass transformations
5. Development of cheap and environment tolerant metal catalysts
6. Green processes in water
7. Oligomerization and dimerization of alkenes
8. Biodegradable polymers
Summary
The primary objective of this bilateral seminar is to bring together chemists from Brazil
and France with complementary, strong and diverse expertises in at least one of the
pillars supporting green chemistry: (i) homogeneous catalysis arising from molecular
metal complexes, including their heterogeneous applications, for clean processes leading
to complex molecules and materials, biomass transformations into useful industrial
intermediates, or biodegradable polymers formation, with energy economy or generation,
(ii) for knowledge improvement to educate young scientists in this growing field and (iii)
to foster bilateral complementary cooperations to better innovate and discover
applications with advanced catalysts, clean synthetic methods, catalytic processes for
industry and thus to build a task force in this catalysis field to the profit of our society. In
a second phase after establishment of cooperations it is our objectives to offer industry
useful interactions.
Résumé
Le principal objectif de ce séminaire bilatéral est de rassembler des chimistes du Brésil
et de France enrichis d’expériences complémentaires fortes et variées dans au moins un
des piliers soutenant la chimie verte : (i) Catalyse homogène issue des complexes
moléculaires de métaux, incluant leurs applications hétérogènes, pour des procédés
propres conduisant à des molécules complexes et de matériaux, la transformation de la
biomasse en intermédiaires industriels utiles, ou la formation de polymères
biodégradables, avec économie en énergie ou pour la génération d’énergie, (ii) pour
l’amélioration des connaissances pour la formation des jeunes scientifiques dans ce
domaine en pleine expansion et (iii) pour favoriser des coopérations bilatérales
complémentaires pour mieux innover et découvrir des applications avec des catalyseurs
performants, des méthodes de synthèse propres, des procédés catalytiques pour
l’industrie, et ainsi pour former une force opérationnelle dans le domaine de la catalyse
pour le bénéfice de notre société. Dans une deuxième phase après l’établissement de
coopérations durables c’est notre objectif d’offrir des intéractions utiles aux industriels.
Resumo
O principal objetivo deste seminário bilateral é reunir os químicos do Brasil e da França,
com especialidades complementares, fortes e diversificadas em pelo menos um dos
pilares de sustentação química verde: (i) catálise homogênea resultante de complexos
metálicos moleculares, incluindo as suas aplicações heterogêneas, para processos
limpos que conduzem a moléculas complexas e materiais, transformações biomassa em
produtos intermediários industriais úteis, ou a formação de polímeros biodegradáveis,
com economia de energia ou da produção, (ii) para a melhoria do conhecimento para
educar jovens cientistas neste campo crescente e (iii) promover bilateral complementar
cooperações para melhor inovar e descobrir aplicações com catalisadores avançados,
métodos sintéticos limpos, processos catalíticos para a indústria e, assim, construir uma
força-tarefa neste campo da catálise para o benefício da nossa sociedade. Numa
segunda fase, após o estabelecimento de cooperações, são os nossos objetivos propor
colaborações úteis ao setor industrial.
Timetable
MONDAY, OCTOBER 19
14:20 - 14:30
BFBW Opening Ceremony
14:30 - 15:00
Pierre H. Dixneuf
The Power of Ruthenium(II) Catalysts for the
Functionalisation of C-H Bonds Even in Water
15:00 - 15:30
Régis Gauvin
Supported Organometallic Catalysis for Improved
Chemical Transformations
15:30 - 16:00
Marc Taillefer
Arylation of Nucleophiles: Recent Progress and
Mechanistic Insight
16:05 - 16:30
Coffee-break
16:30 - 16:50
Katia B. Gusmão
Anchoring Via Covalent Binding of -DiimineNickel Complexes for Catalytic Reactions
16:50 - 17:10
Dalmo Mandeli
Oxidation of Alkanes and Benzene with Hydrogen
Peroxide Catalyzed by Ferrocene in the Presence
of Acids
17:10 - 17:30
Eduardo N. dos Santos
Fine Chemicals from Biomass Employing
Metathesis Reaction
TUESDAY, OCTOBER 20
9:00 - 9:45
Rinaldo Poli
Well-Defined Polymeric Nanoreactors for Biphasic
Catalysis
10:15 - 10:35
Jackson D. Scholten
Synthesis and Catalytic Application of Metal
Nanoparticles in Ionic Liquids
10:35 - 11:00
Coffee-break
11:00 - 11:45
Carlos R. D. Correia
12:15 - 12:35
Mario Meneghetti
Enantioselective Pd-Catalized Heck Arylations
Using Arenediazonium Salts: Is There Anything
Special About Them?
Sn(IV)-Based Organometallics as Catalysts for the
Production of Fatty Acid Alkyl Esters
WEDNESDAY, OCTOBER 21
Sightseeing & free scientific discussions and networking
THURSDAY, OCTOBER 22
9:00 - 9:30
Jean-Francois Carpentier
Stable, Still Highly Reactive Heavy Alkaline- and
Divalent Rare-Earth Complexes for
Hydroelementation Catalysis
9:30 - 10:00
Osvaldo Casagrande Junior
Selective Ethylene Oligomerization with Nickel and
Chromium Catalysts Bearing Bi- and Tridentate Ligands
10:00 - 10:30
Evgueni Kirillov
Propylene Polymerization with Cationic Isoselective
Metallocenes
10:35 - 11:00
Coffee-break
11:00 - 11:30
Christian Bruneau
Metal-Catalyzed Hydrogen Transfer for Green C-H
Bond Functionalization
11:30 - 12:00
Paulo H. Schneider
Palladium-Catalized Synthesis of New Functional
Molecular Materials Containing Chalcogens
12:00 - 12:30
Maryse Gouygou
Phosphole-Complexes in Carbonylation Reactions:
Applications to Natural Products
12:30 - 12:40
BFBW Closing Ceremony
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Prof. Pierre H. Dixneuf
Centre for Catalysis and Green Chemistry
UMR6226: Institut des Sciences Chimiques
Campus de Beaulieu
35042 Rennes Cedex, France
e-mail : [email protected]
tel. : +33 2 23 23 62 80/+33607176660
http://scienceschimiques.Univrennes1.fr/catalyse/personnels/interface/PHD.htm
Research topics:
Homogeneous catalysis and ruthenium in catalysis
Selective formation of C-C bonds with Ru catalysts: alkynes and vinylidenes in catalysis
C-H bond activation/functionalisation, Heterocycle and functional alkene synthesis
Clean processes and Metal-catalysed reactions in water
THE POWER OF RUTHENIUM(II) CATALYSTS
FOR THE FUNCTIONALISATION OF C-H BONDS EVEN IN WATER
Pierre H. Dixneuf*, Percia B. Arockiam, Ferenc Pozgan, Bin Li,
The catalytic sequential activation and functionalisation of inert C-H bonds can now be
promoted by easily to prepare ruthenium(II) catalysts that are stable to air and even water as
shown in review1.
The lecture will show that ruthenium(II) catalysts, associated with carboxylate or phosphate
partners, easily activate arenes and heterocycles by deprotonation of the sp2 C-H bond,2,3 and
that water as solvent increases the activity of ruthenium-carboxylate catalysts.4,5 Examples of CC bond cross-couplings involving functional arene, ferrocene, heterocycle C-H bonds will be
presented, via arylations and dehydrogenative alkenylations.
We can now disclose that water partner and ruthenium(II)-carboxylate catalyst provide the best
cooperative catalytic system to control monoarylation of C-H bonds and to allow mixed
arylations or mixed arylation/alkenylation reactions.
It will be also shown that selected ruthenium(II) catalysts are able to promote the alkylation with
alkenes of unsaturated coordinating ketones in the presence of various alcohols.6
Several directions will be presented for the future of ruthenium(II)-catalysed C-H bond
transformations.
References
1. P. B. Arockiam, C. Bruneau, P. H. Dixneuf, Chem. Rev. 112 (2012) 5879.
2. F. Pozgan, P. H. Dixneuf, Adv. Synth. Catal. 351 (2009) 1737.
3. E. Ferrer-Flegeau, C. Bruneau, P. H. Dixneuf, A. Jutand, J. Am. Chem. Soc. 133 (2011) 10161.
4. P. B. Arockiam, C. Fischmeister, C. Bruneau, P. H. Dixneuf, Angew. Chem. Int. Ed. 49 (2010)
6629
5. B. Li , P. H. Dixneuf Chem. Soc. Rev. 2013, 42 (13), 5744.
6. B. Li, C. Darcel, P. H. Dixneuf, Chem. Commun.,50 ( 2014) 5970.
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Dr. Régis Gauvin
UMR8181: Unité de Catalyse et de Chimie du
Solide
ENSCL-Bât. C7-Cité Scientifique – BP90108
59652 Villeneuve d’Ascq Cedex, France
e-mail: [email protected]
tel.: +33 3 20 43 67 54
http://uccs.univ-lille1.fr/index.php/annuaire/
15-fiches-personnels/159-gauvin-regis
Research topics:
- well-defined supported organometallic catalysts
- structure-activity and -selectivity relationships
- advanced characterization of catalytic materials
SUPPORTED ORGANOMETALLIC CATALYSIS
FOR IMPROVED CHEMICAL TRANSFORMATIONS
R. Gauvin*, T. Vancompernolle, A. Mortreux, L. Delevoye
UMR 8181: Unité de Catalyse et de Chimie du Solide, Catalyse et Synthèses Eco-Compatibles,
Ecole Nationale Supérieure de Chimie de Lille-Université de Lille 1, France.
The immobilization of organometallic species onto inorganic supports holds considerable interest,
as it is expected that the resulting hybrid catalysts would combine the advantages of both
homogeneous and heterogeneous catalysts. This has led to the emergence of surface
organometallic chemistry, a discipline where understanding the surface species’ structure and
drawing structure-activity relationships is of prime importance.1
In this context, well-defined silica-grafted organometallic catalysts have been developed for a
variety of transformations, from fine chemistry to polymerization processes, and significant impact
on catalytic results has been observed. Most particularly in the case of rare-earth metals, the
selectivity of a given transformation differs markedly between the supported catalysts and their
molecular counterparts, with a strong beneficial impact of the immobilization.2,3 Additionally,
grafting of inactive nitrido molybdenum species onto silica triggers activity towards alkyne
metathesis, thanks to stereo-electronic features of the silica host material.4
These selected examples illustrate how, by using a straightforward but rigorously controlled
grafting procedure, immobilization of a given organometallic species can afford a material with
improved catalytic performances.
References:
1. Basset, J.-M.; Psaro, R.; Roberto, D.; Ugo, R. Modern Surface Organometallic Chemistry; WileyVCH: Weinheim, 2009
2. Ajellal, N.; Durieux, G.; Delevoye, L.; Tricot, G.; Dujardin, C.; Thomas, C. M.; Gauvin, R. M.
Chem. Commun. 2010, 46, 1032.
3. Del Rosal, I.; Tschan, M.; Gauvin, R. M.; Maron, L.; Thomas, C.M., Polym. Chem. 2012, 3, 1730.
4. Genelot, M.; Cheval, N. P.; Vitorino, M.; Berrier, E.; Weibel, J.-M.; Pale, P.; Mortreux, A.; Gauvin,
R. M. Chem. Sci. 2013, 4, 2680
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Dr. Marc Taillefer
Institut Charles Gerhardt Montpellier (UMR
5253), AM2N Groupe: Méthodologie de
synthèse moléculaire,
ENSCMontpellier, 8 rue de l'Ecole Normale,
34296, Montpellier. FRANCE
e-mail : [email protected]
Tel : 00 33 (4)67 14 43 52 / (6) 12 86 50 57.
Site Web : http://am2n.enscm.fr/Taillefergroup/Website/Home.html
Research topics:
- Synthesis, reactivity and applications of phosphonium ylides.
- Copper, iron or transition metal free catalyzed arylation of nucleophiles (formation of C-N, C-O,
C-C, C-P bonds) and applications in life sciences. C-H activations, hydroamination reactions,
Piria reaction, catalyzed reduction of unsaturated compounds.
- Mechanistic studies.
-Industrial applications.
ARYLATION OF NUCLEOPHILES:
RECENT PROGRESS AND MECHANISTIC INSIGHT
N-, O-, C- or S-arylation of nucleophiles from aromatic halides occurs with high yields using
original Copper and/or Iron - based catalytic systems.[1-6] Mildness, low cost and simplicity are
features of our methodologies, which make them particularly well suited for industrial scale
syntheses where financial and environmental issues are of greater concern. Within only ten years
a lot of companies adopted this copper technology, which will probably assert its position in the
industry over the next decades. Investigations concerning the mechanism will be also
presented.[7-9]
References
1
2
3
4
5
6
7
8
9
.
H.J. Cristau, P.P Cellier, J.-F. Spindler, M. Taillefer, Chem. Eur. J., 2004, 10, 5607.
M. Taillefer, N. Xia, A. Ouali, Angewandte Chemie, 2007, 46(6), 934.
N. Xia, M. Taillefer, Angewandte Chemie, 2009, 48, 337.
G. Danoun, A. Tlili, F. Monnier, M. Taillefer, Angewandte Chemie, 2012, 51, 12815.
D. Toummini, F. Ouazzani, M. Taillefer, Organic Letters, 2013, 15(7), 1764.
M. Pichette Drapeau, I Fabres, I. Ciofini, L. Grimaud, T. Ollevier, M. Taillefer,
Angewandte Chemie, 2015, 54, DOI:10.1002/anie.201502332.
A. Ouali, J. F. Spindler, A. Jutand, M. Taillefer, Organometallics 2007, 26, 65.
H. Kaddouri, V. Vicente, A. Ouali, F. Ouazzani, M. Taillefer, Angewandte Chemie, 2009,
48, 333.
G. Lefèvre, A. Tlili, M. Taillefer, C. Adamo, I. Ciofini, A. Jutand, Dalton Trans, 2013,
42, 5348.
“Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Dr. Katia Bernardo-Gusmão
Laboratório de Reatividade e Catálise
Instituto de Química - UFRGS
Av. Bento Gonçalves, 9500
Porto Alegre-RS
e-mail: [email protected]
tel.: +55 51 33087240
Research topics:
Homogeneous catalysis
Biphasic Catalysis
Metal complexes heterogenization
Oligomerization/polymerization reactions
ANCHORING VIA COVALENT BINDING OF β-DIIMINE-NICKEL COMPLEXES FOR
CATALYTIC REACTIONS
Katia Bernardo-Gusmão*1, Sibele B.C. Pergher2, Enéderson Rossetto2
1
Laboratório de Reatividade e Catálise, Instituto de Química, Universidade Federal do Rio
Grande do Sul, Porto Alegre, RS, Brazil.
2
Laboratório de Peneiras Moleculares, Instituto de Química, Universidade Federal do Rio
Grande do Norte, Natal, RN, Brazil.
In this Communication anchoring covalent strategies for preparing heterogenized catalysts will be
highlighted. The β-diimine ligands were combined with the alkoxysilane group
chloropropyltrimethoxysilane (CPTMS) and heterogenized on silica using the sol-gel method or
covalently anchored to mesoporous supports (MCM-41 and SBA-15) via interactions with the
silanols of the material matrix and complexed with nickel. The complexes were synthesized for
use in ethylene and propylene oligomerization/polimerization and for comparing the results of
homogeneous and heterogeneous systems. The results of the oligomerization reactions reveal
the influence of the support on the products obtained and this approach has been found helpful
due the ability to reuse and recycle the heterogenized catalyst.
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Dr. Dalmo Mandelli
Centro de Ciências Naturais e Humanas
Universidade Federal do ABC
Avenida dos Estados, 5001 - Bangu
Santo André - SP
Brazil - 92010-580
e-mail: [email protected]
tel.: +55 11 4996-8360
http://lattes.cnpq.br/4005308363836605
Research topics:
Selective oxidation and hydrogenation of organic compounds using homogeneous and
heterogeneous catalysts
Chemical transformations of glycerol: oxidation, etherification, esterification and hydrogenolysis
Metathesis of natural compounds
OXIDATION OF ALKANES AND BENZENE WITH HYDROGEN PEROXIDE CATALYZED BY
FERROCENE IN THE PRESENCE OF ACIDS
Lidia S. Shul’pina1, Aleksandr R. Kudinov1, Dalmo Mandelli2*, Wagner A. Carvalho2,
Yuriy N. Kozlov3, Mikhail M. Vinogradov1, Nikolay S. Ikonnikov1, Georgiy B. Shul’pin3
1
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Russia;
2
Center of Natural and Human Sciences, Federal University of ABC (UFABC), Brazil;
3
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Russia.
Iron complexes, often play roles of good catalysts in the oxidation of saturated and aromatic
hydrocarbons with peroxides, especially with green oxidants such as H2O2.1 In the present work
we report that ferrocene used in catalytic amounts and in the presence of certain acids in low
concentrations very efficiently induces oxidative transformations of alkanes and benzene with
hydrogen peroxide. Here we report that cyclohexane and other alkanes as well as benzene can
be oxidized to the corresponding alkyl hydroperoxides and phenol, respectively, by H2O2 in air in
the presence of catalytic amounts of ferrocene and pyrazine-2-carboxylic acid (PCA). Alkyl
hydroperoxide is relatively stable in the solution, and can be easily reduced by PPh3 to the
corresponding alcohol. The efficient (turnover numbers attained 1200) oxidation of alkanes to
the corresponding alkyl hydroperoxides by H2O2 in the presence of catalytic amounts of
ferrocene proceeds in MeCN at 40-50 ºC. Benzene is oxidized in the same system to phenol.
An obligatory component of the catalytic system for both reactions is pyrazine-2-carboxylic acid
(PCA) or trifluoroacetic acid (TFA). Kinetic study as well as selectivity parameters testified that
the oxidation proceeds with the participation of hydroxyl radicals. In the case of PCA as a cocatalyst the initial rate W0 of the reaction with both cyclohexane and benzene depends
quadratically on [Cp2Fe]0 whereas the two reactions in the presence of TFA are of half order in
ferrocene. The ferrocene-catalyzed reaction of cyclohexane with H216O2 in an atmosphere of
labeled 18O2 gave labeled
cyclohexyl
hydroperoxide containing up to 69% of 18O
(the analysis was by GC-MS) after reduction of cyclohexyl hydroperoxide into cyclohexanol with
PPh3). The authors acknowledge FAPESP (2014/09136-5), CAPES (A017_2013) and
CNPq (472130/2012-9, 311585/2013-2) for supporting the research.
References:
1. Shilov, A. E.; Shul’pin, G. B.. Activation and Catalytic Reactions of Saturated Hydrocarbons in the
Presence of Metal Complexes, Kluwer Academic Publishers, Dordrecht/Boston/London, 2000.
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Prof. Eduardo N. dos Santos
Chemistry Department -ICEx
Federal University of Minas Gerais
31270-901 Belo Horizonte –MG, Brazil
e-mail: [email protected]
tel.: +55 31 34095743
http://lattes.cnpq.br/9246600674685393
Research topics:
Catalysis by Transition Metal Complexes for the valorization of biorenewables
Hydroformylation and Metathesis of C-C double bonds applied to biorenewables
Tandem processes under hydroformylation conditions
Heterogeneization of transition metal complexes catalysts
FINE CHEMICALS FROM BIOMASS EMPLOYING METATHESIS REACTION
Eduardo N. dos Santos
Chemistry Department –ICEx, Federal University of Minas Gerais, 31270-901
Belo Horizonte –MG, Brazil.
Olefin metathesis, now expanded to C-C double bond metathesis, has been one of the most
prominent topics of research in the catalysis by transition metal complexes. Several new drugs
and fine chemicals that came recently to the market employ this methodology in key steps of their
production. Even more striking are the new industrial plants that came recently into stream, in
which palm oil is converted in bulky and intermediate chemical under mild conditions.1 In the last
20 years our group is involved in the study of the transformation of bio-renewables such as
monoterpenes and arylpropenes, which are produced in significant amounts in Brazil, by
transition metal catalysis.2,3 In this talk, results on the transformation of arylpropenes into
compounds of interest for the cosmetic and pharmaceutical industry will be presented. More
specifically, recent results on the cross metathesis of the naturally occurring allylpropenes and
propenylbezenes with alkylacrylates or stilbene derivatives will be discussed.
Acknowledgements to CNPq, CAPES, FAPEMIG, and UMICORE
References:
1. A. Kajetanowicz, A. Sytniczuk, K. Grela, Green Chemistry, 16 (2014) 1579-1585..
2. K.C.B. Oliveira, S.N. Carvalho, M.F. Duarte, E.V. Gusevskaya, E.N. dos Santos, J.E. Karroumi, M.
3.
Gouygou, M. Urrutigoïty, Applied Catalysis A: General, 497 (2015) 10-16.
J.A.M. Lummiss, K.C. Oliveira, A.M.T. Pranckevicius, A.G. Santos, E.N. dos Santos, D.E. Fogg,
Journal of the American Chemical Society, 134 (2012) 18889-18891.
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Prof. Rinaldo Poli
Laboratoire de Chimie de Coordination
UPR8241
205 Route de Narbonne
31077 Toulouse, France
e-mail : [email protected]
tel. : +33-561333173; fax +33-561553003
http://www.lcctoulouse.fr/equipe_g/pages/poli/index.html
Research topics:
Effects of the spin state in organometallic reactivity
Hydrides and dihydrogen complexes
Chiral ligands, their coordination chemistry and catalytic applications.
Homogeneous catalysis: hydrogenation, hydroamination, hydroformylation, C-C cross-coupling
High oxidation state aqueous organometallic chemistry and oxidation catalysis
Metal-mediated controlled radical polymerization
Core-cross-linked micelles and application as nanoreactors in aqueous biphasic catalysis
WELL-DEFINED POLYMERIC NANOREACTORS FOR BIPHASIC CATALYSIS
Rinaldo Poli
Aqueous biphasic catalysis is a most convenient protocol to combine the advantages of
homogeneous catalysis with the possibility to easily recover and recycle the catalyst, but is limited
to the conversion of organic substrates with non-zero water solubility. We have recently
developed an innovative solution consisting of core-cross-linked micelles to yield unimolecular
amphiphilic core-shell catalytic nanoreactors. The presentation will highlight the synthesis and
characterization of these nano-objects and their first catalytic application to the hydroformylation
of 1-octene.1
References
1. (a) X. Zhang, A. F. Cardozo, S. Chen, W. Zhang, C. Julcour, M. Lansalot, J.-F. Blanco, F. Gayet,
H. Delmas, B. Charleux, E. Manoury, F. D’Agosto and R. Poli, Chem. Eur. J., 2014, 20, 15505-15517. (b)
A. F. Cardozo, C. Julcour, L. Barthe, J.-F. Blanco, S. Chen, F. Gayet, E. Manoury, X. Zhang, M. Lansalot,
B. Charleux, F. D’Agosto, R. Poli, H. Delmas, J. Catal. 2015, 324, 1-8. (c) S. Chen, A. F. Cardozo, C.
Julcour, J.-F. Blanco, L. Barthe, F. Gayet, B. Charleux, M. Lansalot, F. D’Agosto, H. Delmas, E. Manoury,
R. Poli, Polymer 2015, 72, 327-335.
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Dr. Jackson D. Scholten
Institute of Chemistry - UFRGS
Av. Bento Gonçalves, 9500, Agronomia,
91501-970, Porto Alegre - RS, Brazil.
e-mail: [email protected]
tel.: +55 51 3308 9633
www.iq.ufrgs.br
Research topics:
Synthesis of nanoparticles from organometallic precursors or by sputtering deposition
(Photo)catalytic application of nanoparticles in hydrogenation reactions and for sustainable
energy production
Activation of small molecules by photocatalysis
SYNTHESIS AND CATALYTIC APPLICATION OF METAL NANOPARTICLES IN IONIC
LIQUIDS
Jackson D. Scholten
Institute of Chemistry - UFRGS, Porto Alegre - RS, Brazil
Metal nanoparticles with a small size and narrow size distribution can be prepared by the
chemical reduction/decomposition reaction of organometallic complexes or via physical
approach, such as the sputtering method.1 Due to their thermodynamic tendency to form
aggregates, these nanoparticles shall be kinetically stabilized in solution with the presence of
proper stabilizing ligands or by deposition onto classical supports.2 In this context, ionic liquids
became a suitable class of solvents that can be used for the stabilization of metal nanoparticles
as well as recyclable media for catalytic transformations.3 The wide applicability of these
nanoclusters includes hydrogenation of unsaturated bonds, hydroformylation of olefins, FischerTropsch synthesis and photocatalysis.
The author thanks CAPES and CNPq for the financial support.
References:
1. Dupont, J; Scholten, J. D.; Chem. Soc. Rev., 2010, 39, 1780.
2. Scholten, J. D.; Curr. Org. Chem., 2013, 17, 348.
3. Scholten, J. D.; Leal, B. C.; Dupont, J.; ACS Catal., 2012, 2, 184.
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Prof. Carlos Roque D. Correia
Chemistry Institute
State University of Campinas - UNICAMP
Campinas, 13083-970, Sao Paulo,
Brazil
e-mail : [email protected]
tel. : +55 19 3521 3086
http://www.correia-group.com
Research topics:
Homogeneous catalysis with emphasis on palladium-catalyzed reactions
Development of new and practical synthetic methodologies
Ligand design for enantioselective metal-catalyzed reactions
Synthesis of heterocyclic natural or unnatural compounds of medicinal interest
ENANTIOSELECTIVE Pd-CATALIZED HECK ARYLATIONS USING ARENEDIAZONIUM
SALTS: IS THERE ANYTHING SPECIAL ABOUT THEM?
Carlos Roque D. Correia*, Caio C. Oliveira, Juliana M. Oliveira, Ricardo A. Angnes, Rafaela C.
Carmona
The enantioselective arylation of olefins (Heck reaction) has been the subject of intense studies
in the last decades because of its outstanding potential to generate new drugs, functional
materials, fragrances, and other important compounds.
In this context, the palladium catalyzed coupling of arenediazonium salts to olefins (HeckMatsuda reaction)1 represents a robust method to access complex intermediates for the
synthesis of functional and bioactive molecules. The Heck-Matsuda arylations are often milder,
much faster and easier to carry out than the conventional Heck protocols. However, in spite of its
many advantages and long-term existence, its enantioselective version went unreported until
2012.2 Its development constituted a considerable synthetic challenge mainly because of the
intrinsic incompatibility between phosphine ligands and the electrophilic arenediazonium salts.
This lecture will present recent results from my laboratory to perform effective and practical
asymmetric Heck-Matsuda reactions employing chiral, N,N-ligands in desymmetrization
reactions,3 generation of challenging chiral tetrasubstituted tertiary centers, and quaternary
stereogenic centers, together with application in the enantioselective total synthesis of drugs.4
References
1. Reviews: (a) Taylor, J. G.; Moro, A. V.; Correia, C. R. D. Eur. J. Org. Chem. 2011, 1403–1428.(b)
Felpin, F.-X.; Nassar-Hardy, L.; Le Callonnec, F.; Fouquet, E. Tetrahedron 2011, 67, 2815–2831.
2. (a) Correia, C. R. D.; Oliveira, C. C.; Salles Jr. A. G.; Santos, A. F. Tetrahedron Lett. 2012, 53,
3325-3328, (b) Oliveira, C. C.; Angnes, R. A.; Correia, C. R. D. J. Org. Chem. 2013, 78, 4373-4385.
(c) Werner, E. W.; Mei, T.-S.; Burckle, A. J.; Sigman, M. S. Science 2012, 338, 1455–1458.
3. (a) Angnes, R. A.; Oliveira, J. M.; Oliveira, C. C.; Martins, N. C.; Correia, C. R. D. Chemistry – A
European Journal, 2014, 20, 13117–13121, (b) Carmona, R. C.; Correia, C. R. D. Adv. Synth. Cat.
2015, 357, 2639-2643.
4. Oliveira, C. C; Pfaltz, A.; Correia, C. R. D. C Angew. Chem Int. Ed. 2015, accepted
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Prof. Dr. Mario Roberto Meneghetti
Grupo de Catálise e Reatividade Química
Instituto de Química e Biotecnologia
Universidade Federal de Alagoas
CEP 57072-970, Maceió, AL, Brazil
e-mail: [email protected]
tel.: +55 82 3214 1744
lattes.cnpq.br/6642503680426310 Research topics:
Oil chemistry
Organometallic chemistry
Synthesis of anisotropic nanoparticles
Sn(IV)-BASED ORGANOMETALLICS AS CATALYSTS FOR THE PRODUCTION OF FATTY
ACID ALKYL ESTERS
M. R. Meneghetti, S. M. Plentz Meneghetti
Grupo de Catálise e Reatividade Química, Instituto de Química e Biotecnologia, Universidade
Federal de Alagoas, CEP 57072-970, Maceió, AL, Brazil.
Transesterification reactions have been investigated using these organometallic Sn(IV)
complexes while varying several parameters, having soybean or castor oils as sources of fats,
and various alcohols. The results from reactions conducted under reflux conditions gave lower
yields in comparison with those obtained using a closed steel reactor, in which more severe
reaction conditions can be attained. The explanation for this behavior can be traced to: (i) the
amount of methanol present in the liquid phase inside a closed steel reactor (approximately 90–
96%), compared with only 35% using a reactor operating under reflux conditions, and (ii) the
higher degree of solubility and activation of the catalysts that can be reached at higher
temperatures inside the steel reactor.1,2
Esterification reactions of soybean FAs with methanol (and in some cases with ethanol) in the
presence of these organotin(IV) complexes have been also investigated under different reaction
conditions, using the molar ratio 400 : 100 : 1 (alcohol : FA : catalyst).3 All complexes were
found to be active because in their presence better conversions were observed when compared
with the self-catalyzed reaction. When the reaction temperature was increased even better
results were obtained.
The authors acknowledge the financial support from Brazilian research founding agencies:
FINEP, CNPq, FAPEAL, and also INCT-Catalise. MRM and SMPM thank CNPq for research
fellowships.
References:
1. D. R. de Mendonca, J. P. V. da Silva, R. M. de Almeida, C. R. Wolf, M. R. Meneghetti and S. M.
P. Meneghetti, Appl. Catal., A, 2009, 365, 105.
2. D. A. C. Ferreira, M. R. Meneghetti, S. M. P. Meneghetti and C. R. Wolf, Appl. Catal., A, 2007,
317, 58.
3. Y. C. Brito, D. A. C. Ferreira, D. M. A. Fragoso, P. R. Mendes, C. M. J. de Oliveira, M. R.
Meneghetti and S. M. P. Meneghetti, Appl. Catal., A, 2012, 443, 202.
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Pr. Jean-François CARPENTIER
UMR 6226: Institut des Sciences Chimiques
de Rennes
Campus de Beaulieu
35042 Rennes Cedex, France
e-mail: [email protected]
tel.: +33 2 23 23 59 50
http://scienceschimiques.univrennes1.fr/catalyse/carpentier/index.html
Research topics:
Organometallic chemistry of oxophilic elements (groups 2-6, 12(14)
Design of single-site (stereoselective) polymerization catalysts:
Homogeneous catalysis for fine chemicals synthesis
Green chemistry and biorenewables, biodegradable polymer materials
STABLE, STILL HIGHLY REACTIVE HEAVY ALKALINE- AND DIVALENT RARE-EARTH
COMPLEXES FOR HYDROELEMENTATION CATALYSIS
Bo Liu, Sorin Rosca, Yann Sarazin, and Jean-François Carpentier*
Organometallics, Materials and Catalysis laboratories, Institut des Sciences Chimiques de Rennes,
UMR 6226 CNRS – University of Rennes 1, Rennes, 35042 Cedex, France;
Means to stabilize complexes of the large, oxophilic and benign alkaline-earth metals (Ae = Ca, Sr
and Ba) against ligand scrambling have become available, and as a result the interest in the reactivity
of these main group metals is rising sharply. We have shown that non-covalent interactions such as
Ae•••H–Si and Ae•••F–C afford stable, yet highly reactive complexes which catalyze polymerization
and hydroelementation reactions.[1-3] The preparation of families of heteroleptic alkyl and amide
complexes will be presented here, highlighting the importance of the ancillary ligand and Ae•••H–Si
agostic bonding in their stability.[2,3,4] The reactivity of the new Ae complexes is examined in
relation with four key organic transformations leading to C–P and C–N bond formation: ketone hydrophosphonylation,[5] intermolecular and hydroamination and hydrophosphination of activated
alkenes, [3,6] and cyclohydroamination of amino-alkenes.[4,6,7] Intermolecular alkene
hydroamination and hydrophosphination give
strictly anti-Marko-vnikov products, and the
catalytic activity systematically increases with
metal size: Ca < Sr < Ba. Key structurereactivity trends will be discussed in light of
kinetic and mechanistic investigations. The
hydrophosphination of alkenes with catalysts
based on divalent lanthanides, which are
closely related to Ae elements, will be
discussed as well [8].
References:
[1]
[2]
[3]
[4]
[5]
[6]
[7]
Y. Sarazin, B. Liu, T. Roisnel, L. Maron, J.-F. Carpentier, J. Am. Chem. Soc., 2011, 133, 9069.
B. Liu, T. Roisnel, J.-P. Guégan, J.-F. Carpentier, Y. Sarazin, Chem. Eur. J., 2012, 18, 6289.
B. Liu, T. Roisnel, J.-F. Carpentier, Y. Sarazin, Angew. Chem. Int. Ed., 2012, 51, 4943.
B. Liu, T. Roisnel, J.-F. Carpentier, Y. Sarazin, Chem. Eur. J., 2013, 19, 2784.
B. Liu, J.-F. Carpentier, Y. Sarazin, Chem. Eur. J., 2012, 18, 13259.
B. Liu, T. Roisnel, J.-F. Carpentier, Y. Sarazin, Chem. Eur. J. 2013, 19, 13445.
N. Romero, S.-C. Roşca, Y. Sarazin, J.-F. Carpentier, L. Vendier, S. Mallet-Ladeira, C. Dinoi, M. Etienne, Chem. Eur.
J. 2015, 21, 4115.
[8] I. V. Basalov, S. C. Roşca, D. M. Lyubov, A. N. Selikhov, G. K. Fukin, Y. Sarazin, J.-F. Carpentier, A. A. Trifonov,
Inorg. Chem. 2014, 53, 1654.
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Prof. Osvaldo L. Casagrande Jr
Laboratory of Molecular Catalysis
Instituto de Química - UFRGS
Av. Bento Gonçalves, 9500, Porto Alegre,
RS, 91501-970, Brazil
e-mail : [email protected]
tel. : +55 51 3308.9629/+55 51 3308.9624
http://www.iq.ufrgs.br/lamoca/faculty.htm
Research topics:
Organometallic Chemistry involving groups 4-6, and 10
Homogeneous Catalysis
Polymerization and Oligomerization Catalysis:
Lighter -Olefins
Polyolefins,
PE
Nanocomposites,
SELECTIVE ETHYLENE OLIGOMERIZATION WITH NICKEL AND CHROMIUM CATALYSTS
BEARING BI- AND TRIDENTATE LIGANDS
O. L. Casagrande Jra,*, A. C. Pinheiro,a A. H. D. P. S Ulbrich,a E. Kirillov and b J-F. Carpentierb
a
Laboratory of Molecular Catalysis, Instituto de Química, Universidade Federal do Rio Grande
do Sul, Av. Bento Gonçalves, 9500, Porto Alegre, RS 90501-970, Brazil
b
Institut des Sciences Chimiques de Rennes, Organometallics: Materials and Catalysis Dept.,
UMR 6226 CNRS-Université de Rennes 1, F-35042 Rennes Cedex,
A considerable amount of research effort has been dedicated both recently and in the past to
nonselective ethylene oligomerization with the aim of improving the understanding of this industrially
relevant catalytic process.i The mixtures of linear alpha olefins (LAO) produced by this process are in fact
valuable commodity chemicals for a range of industrial and household applications depending on their
molar mass distribution (detergents, surfactants, cosmetics, synthetic lubricants, etc). ii Herein, we
describe the synthesis, structural characterization of Ni(II) and Cr(III) complexes bearing bi- and tridentate
ligands and their use in ethylene oligomerization. We will be also present some discuss related to the
performance of these precatalysts, evaluating the role of the ligand, and the experimental parameters
(cocatalyst type, temperature, and oligomerization time) on the activity and on the product distribution
(oligomer/PE ratio).
This work was supported in part by the Petrobras S/A, CAPES, French MESR, and CNRS. The authors
are grateful to CAPES-COFECUB for joined Action 804/14 and CAPES-CNRS for joined action
PICS05923.
References
i
ii
(a) D. S. McGuinness, V. C. Gibson and J. W. Steed, Organometallics, 2004, 23, 6288; (b) K. Tenza, M. J. Hanton and A. M. Z.
Slawin, Organometallics, 2009, 28, 4852; (c) E. Kirillov, T. Roisnel, A. Razavi and J.-F. Carpentier, Organometallics, 2009, 28,
2401; (d) N. Ajellal, M. C. A. Kuhn, A. D. G. Boff, M. Hoerner, C. M. Thomas, J.-F. Carpentier and O. L. Casagrande,
Organometallics, 2006, 25, 1213;(e) F. Junges, M. C. A. Kuhn, A. H. D. P. dos Santos, C. R. K. Rabello, C. M. Thomas, J.-F.
Carpentier and O. L. Casagrande Jr., Organometallics, 2007, 26, 4010; (f) Y. Chen, W. Zuo, P. Hao, S. Zhang, K. Gao and W.H. Sun, J. Organomet. Chem., 2008, 693, 750; (g) R. Gao, T. Liang, F. Wanga and W.-H. Sun, J. Organomet. Chem., 2009,
694, 3701; (h) B. L. Small, R. Rios, E. R. Fernandez, D. L. Gerlach, J. A. Halfen and M. J. Carney, Organometallics, 2010, 29,
6723. (i) A. C. Pinheiro, E. Kirillov T. Roisnel, J.-F. Carpentier, O. L. Casagrande Jr, Dalton Trans., 2015, 44, 16073-16080. (j)
A. H. D. P. S. Ulbrich, J. S. Milani, E. Kirillov T. Roisnel, J.-F. Carpentier, O. L. Casagrande Jr, New J. of Chem, 2015, 39, 7234.
(a) P.W.N.N. Van Leeuwen, Homogeneous Catalysis, Kluwer Academic, Inc. Dordrecht, 2004, p 175; (b) D. Vogt,
Oligomerization of ethylene to higher linear Rolefins. In Applied Homogeneous Catalysis with Organometallic Compounds, Eds.,
Wiley-VCH: Weinheim, Germany, 2000, p 245; (c) G. R. Lappin and J. D.Sauer, in Alpha Olefins Application Handbook, Marcel
Dekker: New York, 1989, Vol. 37, p 1.
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Evgueni Kirillov
Centre for Catalysis and Green Chemistry
UMR6226: Institut des Sciences Chimiques
Campus de Beaulieu
35042 Rennes Cedex, France
e-mail : [email protected]
tel. : +33 2 23 23 61 18
http://scienceschimiques.univrennes1.fr/catalyse/carpentier/files_links/Grou
pMembers/EK_files/personal/evgueni_kirillov.h
tml
Research topics:
• Organometallic, coordination chemistry
• Polymerization catalysis with metallocenes and post-metallocenes
• "Oscillating" polymerization catalysis
• Polynuclear polymerization catalysis
• Stereochemistry of polymerization
• Prediction of chemical reactions using quantum mechanics methods
• Mechanistic studies of elementary steps in polymerization reactions
• Activation of CO2 via coupling with unsaturated substrates
PROPYLENE POLYMERIZATION WITH CATIONIC ISOSELECTIVE METALLOCENES
Evgueni Kirillov*, Jean-François Carpentier, Gabriel Theurkauff, Manuela Bader, Nicolas
Marquet
Single-site group 4 metallocene systems are intensely used for the production of isotactic
polypropylene (iPP) (and iPP-based olefinic copolymers),1 which is one of the landmarks of the
plastics market with a global annual production of ca. 45 MT.
In this study, solution and in the solid state of mono- and heterobimetallic ion-pairs of
isoselective zirconocenes incorporating different counteranions ([MeB(C6F5)3], [B(C6F5)4],
[“MeMAO”]) have been investigated.2 Details of the stability, dynamics and interconversion of
ion pairs, as well as their behavior in isoselective polymerization of propylene and structureactivity relationship will be discussed.
The authors are grateful to Total Raffinage-Chimie for the financial support of this work.
References
1. (a) Kirillov, E.; Marquet, N.; Bader, M.; Razavi, A.; Belia, V.; Hampel, F.; Roisnel, T.; Gladysz, J.
A. ; Carpentier, J.-F. Organometallics 2011, 30, 263. (b) Kirillov, E.; Marquet, N.; Razavi, A.; Belia,
V.; Hampel, F.; Roisnel, T.; Gladysz, J. A. ; Carpentier, J.-F. Organometallics 2010, 29, 5379. (c)
Bader, M.; Marquet, N.; Kirillov, E.; Roisnel, T.; Razavi, A.; Lhost, O.; Carpentier, J.-F.
Organometallics 2012, 21, 8375.
2. (a) Theurkauff, G.; Bondon, A.; Dorcet, V.; Carpentier, J.-F.; Kirillov, E. Angew. Chem. Int. Ed.
2015, 54, 6343. (b) Theurkauff, G.; Roisnel, T.; Waassenaar, J.; Carpentier, J.-F.; Kirillov, E.
Macromol. Chem. Phys. 2014, 215, 2035.
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Dr. Christian Bruneau
UMR6226: Institut des Sciences Chimiques
de Rennes
Campus de Beaulieu
35042 Rennes Cedex, France
e-mail: [email protected]
tel.: +33 2 23 23 62 83
http://scienceschimiques.univ-rennes1.fr/catalyse/
personnels/interface/CB.ht
Research topics:
Design and synthesis of efficient molecular catalysts
C-H bond activation/functionalization for C-C bond formation
Olefin metathesis: catalysts and applications in biomass transformations
Hydrogen transfer and enantioselective hydrogenation
METAL-CATALYZED HYDROGEN TRANSFER FOR GREEN C-H BOND
FUNCTIONALIZATION
C. Bruneau*, M. Achard, B. Sundararaju, F. Jiang
UMR 6226 : Institut des Sciences Chimiques de Rennes, Organométalliques : Matériaux et
Catalyse, Université de Rennes 1, France.
New ruthenium and iridium complexes featuring a bidentate phosphinesulfonate ligand have
shown high efficiency in catalytic transformations of alcohols and amines involving hydrogen
transfer processes.1 Taking advantage of this reactivity, catalytic tandem processes to
functionalize the sp3C(3)-H bond of saturated cyclic amines in order to get access to various
C(3)-alkylated amines have been developed.2,3 Starting from cyclic saturated amines, reactions
with alcohols or aldehydes selectively led to C(3)-substituted cyclic amines with formation of
water as the sole byproduct.
Tandem catalytic transformations initiated by C-N and C-C bond formation involving H-transfer
processes followed by cyclization reactions have led to a variety of polycyclic amines.Thus,
julolidine derivatives resulting from a sequence of N-alkylation followed by electrocyclization
have been obtained from tetrahydroquinolines and propane-1,3-diols.3 The reaction of
salicylaldehyde with tertiary saturated cyclic amines offered straightforward accesses to various
types of heterocycles.4 All these catalytic tandem reactions produced only water as byproduct.
The authors acknowledge the Indo-French CEFIPRA joint project for a fellowship to B. S. and
the European SYNFLOW network for a financial support to F. J.
References:
1. Sundararaju, B.; Tang, Z.; Achard, M.; Sharma, G. V. M.; Toupet, L.; Bruneau, C.; Adv. Synth.
Catal., 2010, 352, 3141.
2. Sundararaju, B.; Achard, M.; Sharma, G. V. M.; Bruneau, C.; J. Am. Chem. Soc., 2011, 133,
103401.
3. Labed, A.; Jiang, F.; Labed, I.; Lator, A.; Peters, M.; Achard, M.; Kabouche, A.; Kabouche, Z.;
Sharma, G. V. M.; Bruneau, C.; ChemCatChem, 2015, 7, 1090.
4. Jiang, F.; Achard, M.; Bruneau, C.; Chem. Eur. J., 2015, 21,.in press
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Dr. Paulo Henrique Schneider
Institute of Chemistry
Federal University of Rio Grande do Sul
91501-970, POBox 15003
Porto Alegre, RS, Brazil
e-mail: [email protected]
tel.: +55 51 3308 9636
Research topics:
Organic synthesis and catalysis
Organocatalysis
Asymmetric synthesis
Development of new reaction methodologies
PALLADIUM-CATALIZED SYNTHESIS OF NEW FUNCTIONAL
MOLECULAR MATERIALS CONTAINING CHALCOGENS
Paulo Henrique Schneider
The research in our group is centered on the field of organic synthesis and catalysis. We
are interested in new concepts in synthetic organic chemistry involving organocatalysis,1 metalmediated catalysis, synthesis and evaluations of the properties of organochalcogen
compounds2 as well as on the development of new reaction methodologies.3
Herein we are going to present our latest results on the palladium-catalyzed direct
arylation of selenophenes, establishing an efficient and convenient method for the
regioselective formation of 2-aryl or 2,5-diaryl selenophenes. The scope and limitations, as well
as a mechanistic study will be discussed.4 Some preliminary results on the alkynilation of
selenophenes will also be presented.
The authors acknowledge to UFRGS, CAPES, CNPq, INCT-CMN and FAPERGS for financial
and technical support.
References:
1.
Rambo, R. S.; Jacoby, C. G.; da Silva, T. L.; Schneider, P. H., Tetrahedron-Asymmetr
2015, 26 (12-13), 632-637.
2.
aRampon, D. S.; Rodembusch, F. S.; Schneider, J. M. F. M.; Bechtold, I. H.; Goncalves,
P. F. B.; Merlo, A. A.; Schneider, P. H., J Mater Chem 2010, 20 (4), 715-722; bRampon, D. D.;
Santos, F. D.; Descalzo, R. R.; Toldo, J. M.; Goncalves, P. F. B.; Schneider, P. H.;
Rodembusch, F. S., J Phys Org Chem 2014, 27 (4), 336-343.
3.
Rampon, D. S.; Giovenardi, R.; Silva, T. L.; Rambo, R. S.; Merlo, A. A.; Schneider, P. H.,
Eur J Org Chem 2011, (35), 7066-7070.
4.
Rampon, D. S.; Wessjohann, L. A.; Schneider, P. H., J. Org. Chem. 2014, 79 (13), 59875992.
Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”
19-22 October 2015, Angra dos Reis – RJ, Brazil
Dr. Maryse GOUYGOU
UPR 8241: Laboratoire de Chimie
Coordination du CNRS
205 Route de Narbonne BP 44099
31077 Toulouse Cedex 04
e-mail: [email protected]
tel.: +33 5 34 32 35 77
de
http:// www.lcc-toulouse.fr/lcc/spip.php?article265
Research topics:
Development of (chiral) phosphorus ligands and molecular catalysts
(Enantio)selective homogeneous catalysis: hydrogenation (Rh, Ir), hydroformylation (Rh),
hydroaminomethylation (Rh), cyclocarbonylation (Pd) and cycloisomerisation ( Pt, Au)
Functionalisation of natural substrates
PHOSPHOLE-COMPLEXES IN CARBONYLATION REACTIONS:
APPLICATIONS TO NATURAL PRODUCTS
M. Gouygou*, J. ElKarroumi, A. Oukhrib, M. Urrutigoïty, K. C. B Oliveira, E. N. Gusevskaya,
E. N. Dos Santos
Transition metal catalyzed hydroformylation sequence represent a powerful tool for the production
of aldehydes that can be further converted into other valuable products. Following a general trend
in green chemistry, hydroformylation reactions have become an integral part of tandem or
dominos sequences.1
Phosphole-based catalysts, initially introduced in catalytic hydroformylation reactions, were and
are still being exploited in many metallo-catalyzed reactions.2 Taking advantage of their
performance in hydroformylation, catalytic tandem reaction sequences under hydroformylation
conditions have been developed. Rhodium phosphole complexes effect efficient tandem
hydroformylation/reductive amination3 and hydroformylation/acetalisation reactions,4 whereas
palladium complexes are able to promote carbonylation/cyclisation reaction.5 Examples of
functionalisation of natural substrates will be presented.
The authors acknowledge CNRS and CAPES-COFECUB for financial support to this work.
References:
1. Eilbracht, P.; Schmidt, A. M.; Top. Organomet. Chem., 2006, 18, 65.
2. Fourmy, K.; Nguyen, D. C.; Dechy-Cabaret O.; Gouygou M.; Catalysis Science & Technology,
2015, 5, 4289.
3. Oliveira, K. C. B., Carvalho, S. N., Duarte, M. F.; Gusevskaya, E. V.; dos Santos, ,E. N.; Elkarroumi,
J.; Gouygou, M. Urrutigoïty, M.; Applied Catalysis A: General, 2015, 497, 10.
4. Oukhrib, A.; Benharref, A.; Gouygou, M.; Urrutigoïty, M.; submitted
5. Elkarroumi, J.; Elhaib, A.; Manoury, E.; Benharref, A.; Daran, J. C.; Gouygou, M.; Urrutigoïty, M.;
J. Mol. Cat., 2015, 401, 18.