October 19-22, 2015 Angra dos Reis RJ, Brazil BOOK OF ...silqcom2015.com.br/arquivos/BFBW_Book.pdf19...

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 -Diimine-

Nickel 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


11:00 - 11:45 Carlos R. D. Correia Enantioselective Pd-Catalized Heck Arylations Using Arenediazonium Salts: Is There Anything

Special About Them?

12:15 - 12:35 Mario Meneghetti 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


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.Univ-rennes1.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 C-C 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; Wiley-VCH: 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



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/Taillefer-

group/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 H.J. Cristau, P.P Cellier, J.-F. Spindler, M. Taillefer, Chem. Eur. J., 2004, 10, 5607.

2 M. Taillefer, N. Xia, A. Ouali, Angewandte Chemie, 2007, 46(6), 934.

3 N. Xia, M. Taillefer, Angewandte Chemie, 2009, 48, 337.

4 G. Danoun, A. Tlili, F. Monnier, M. Taillefer, Angewandte Chemie, 2012, 51, 12815.

5 D. Toummini, F. Ouazzani, M. Taillefer, Organic Letters, 2013, 15(7), 1764.

6 M. Pichette Drapeau, I Fabres, I. Ciofini, L. Grimaud, T. Ollevier, M. Taillefer,

Angewandte Chemie, 2015, 54, DOI:10.1002/anie.201502332.

7 A. Ouali, J. F. Spindler, A. Jutand, M. Taillefer, Organometallics 2007, 26, 65.

8 H. Kaddouri, V. Vicente, A. Ouali, F. Ouazzani, M. Taillefer, Angewandte Chemie, 2009,

48, 333.

9 G. Lefèvre, A. Tlili, M. Taillefer, C. Adamo, I. Ciofini, A. Jutand, Dalton Trans, 2013,

42, 5348.

.

mailto:[email protected]

http://am2n.enscm.fr/Taillefer-group/Website/Home.html

http://am2n.enscm.fr/Taillefer-group/Website/Home.html

“Brazil-France bilateral workshop “Organometallic Catalysis for Green and Sustainable Chemistry”


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

1Laboratório de Reatividade e Catálise, Instituto de Química, Universidade Federal do Rio

Grande do Sul, Porto Alegre, RS, Brazil.

2Laboratório 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.



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

1Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Russia; 2Center of Natural and Human Sciences, Federal University of ABC (UFABC), Brazil;

3Semenov 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 co-catalyst 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 H2

16O2 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.



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.

Gouygou, M. Urrutigoïty, Applied Catalysis A: General, 497 (2015) 10-16. 3. 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.



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.lcc-toulouse.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.


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, Fischer-Tropsch 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.



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 (Heck-

Matsuda 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


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.



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.univ-rennes1.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 hydro-

phosphonylation,[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 structure-

reactivity 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] Y. Sarazin, B. Liu, T. Roisnel, L. Maron, J.-F. Carpentier, J. Am. Chem. Soc., 2011, 133, 9069. [2] B. Liu, T. Roisnel, J.-P. Guégan, J.-F. Carpentier, Y. Sarazin, Chem. Eur. J., 2012, 18, 6289. [3] B. Liu, T. Roisnel, J.-F. Carpentier, Y. Sarazin, Angew. Chem. Int. Ed., 2012, 51, 4943. [4] B. Liu, T. Roisnel, J.-F. Carpentier, Y. Sarazin, Chem. Eur. J., 2013, 19, 2784. [5] B. Liu, J.-F. Carpentier, Y. Sarazin, Chem. Eur. J., 2012, 18, 13259. [6] B. Liu, T. Roisnel, J.-F. Carpentier, Y. Sarazin, Chem. Eur. J. 2013, 19, 13445. [7] 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.



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: Polyolefins, PE Nanocomposites,

Lighter -Olefins

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

aLaboratory of Molecular Catalysis, Instituto de Química, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves, 9500, Porto Alegre, RS 90501-970, Brazil

bInstitut 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 (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.

ii (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.

http://www.iq.ufrgs.br/lamoca/faculty.htm



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.univ-rennes1.fr/catalyse/carpentier/files_links/GroupMembers/EK_files/personal/evgueni_kirillov.html

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],

[“MeMAO”]) 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 structure-

activity 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.

http://scienceschimiques.univ-rennes1.fr/catalyse/carpentier/files_links/GroupMembers/EK_files/personal/evgueni_kirillov.html%20%0c





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


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 metal-mediated 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), 5987-5992.



Dr. Maryse GOUYGOU UPR 8241: Laboratoire de Chimie de Coordination du CNRS 205 Route de Narbonne BP 44099 31077 Toulouse Cedex 04 e-mail: [email protected] tel.: +33 5 34 32 35 77 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.

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