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1. Cross metathesis of unsaturated epoxides for the synthesis of polyfunctional building blocks

Author

Meriem K. Abderrezak, Kristýna Šichová, Nancy Dominguez-Boblett, Antoine Dupé, Zahia Kabouche, Christian Bruneau, and Cédric Fischmeister

Subjects
cross metathesis, epoxide, ruthenium catalysts, tandem reactions, Science, Organic chemistry, QD241-441
Abstract

The cross metathesis of 1,2-epoxy-5-hexene (1) with methyl acrylate and acrylonitrile was investigated as an entry to the synthesis of polyfunctional compounds. The resulting cross metathesis products were hydrogenated in a tandem fashion employing the residual ruthenium from the metathesis step as the hydrogenation catalyst. Interestingly, the epoxide ring remained unreactive toward this hydrogenation method. The saturated compound resulting from the cross metathesis of 1 with methyl acrylate was transformed by means of nucleophilic ring-opening of the epoxide to furnish a diol, an alkoxy alcohol and an amino alcohol in high yields.

Published
2015
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2. Pierre Dixneuf: A Pioneering Career in Organometallic Chemistry Highlighting Ruthenium as a Star Metal in Homogeneous Catalysis

Author

Christophe Darcel, Jean-François Soulé, Christian Bruneau, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, Homogeneous catalysis, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ruthenium, Inorganic Chemistry, Metal, chemistry.chemical_compound, chemistry, visual_art, Polymer chemistry, visual_art.visual_art_medium, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Organometallic chemistry
Abstract

International audience

Published
2021
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5. N-Heterocyclic carbene–palladium catalysts for the direct arylation of pyrrole derivatives with aryl chlorides

Author

Ismail Özdemir, Nevin Gürbüz, Nazan Kaloğlu, Öznur Doğan, Murat Kaloğlu, Christian Bruneau, and Henri Doucet

Subjects
aryl chlorides, atom-economy, C–H bond activation, C–H functionalization, carbenes, palladium, pyrroles, Science, Organic chemistry, QD241-441
Abstract

New Pd–NHC complexes have been synthesized and employed for palladium-catalyzed direct arylation of pyrrole derivatives by using electron-deficient aryl chlorides as coupling partners. The desired coupling products were obtained in moderate to good yields by using 1 mol % of these air-stable palladium complexes. This is an advantage compared to the procedures employing air-sensitive phosphines, which have been previously shown to promote the coupling of aryl chlorides with heteroarenes.

Published
2013
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6. Ruthenium Catalyzed Regioselective β‐C( sp 3 )−H Functionalization of N ‐Alkyl‐ N′ ‐ p– nitrophenyl Substituted Piperazines using Aldehydes as Alkylating Agents

Author

Mathieu Achard, Christian Bruneau, V. Murugesh, Gangavaram V. M. Sharma, Surisetti Suresh, and Apurba Ranjan Sahoo

Subjects
chemistry.chemical_classification, Nucleophilic addition, 010405 organic chemistry, chemistry.chemical_element, Regioselectivity, General Chemistry, Alkylation, 010402 general chemistry, 01 natural sciences, Aldehyde, Medicinal chemistry, 0104 chemical sciences, Ruthenium, Enamine, Piperazine, chemistry.chemical_compound, chemistry, lipids (amino acids, peptides, and proteins), Alkyl
Abstract

Herein, we disclose a ruthenium-catalyzed regioselective beta-C(sp(3))-H bond functionalization on the piperazine core using aldehydes as alkylating agents. The present transformation appears to go through the dehydrogenation of the piperazine to propagate to enamine in situ, followed by nucleophilic addition to the aldehyde and hydrogenation to result in the regioselective beta-C(sp(3))-H alkylation. A variety of aromatic, heteroaromatic, aliphatic aldehydes were employed for the C-3 alkylation of N-alkyl-N '-p-nitrophenyl substituted piperazines.

Published
2020
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7. Acceptorless and Base-Free Dehydrogenation of Alcohols Mediated by a Dipyridylamine-Iridium(III) Catalyst

Author

Cédric Fischmeister, Harikrishnan Jayaprakash, Shengdong Wang, Liwei Guo, and Christian Bruneau

Subjects
Reaction mechanism, 010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, Homogeneous catalysis, 010402 general chemistry, Anisole, 01 natural sciences, Toluene, 0104 chemical sciences, Catalysis, Ruthenium, chemistry.chemical_compound, chemistry, Polymer chemistry, Dehydrogenation, Iridium, Physical and Theoretical Chemistry
Abstract

Several dipyridylamine-Ir(III)and dipyridylamine-Ru(II)complexes have been evaluated in the acceptorless dehydrogenation of alcohols in the absence of base additives. Iridium catalysts were found superior to ruthenium complexes, and the nature of the bridging nitrogen in dipyridylamine ligands was also evidenced as a key parameter. Catalytic reactions were conducted in toluene, but more sustainable solvents such as anisole andp-cymene were found suitable for this transformation.

Published
2020
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8. Ene–yne cross-metathesis with ruthenium carbene catalysts

Author

Cédric Fischmeister and Christian Bruneau

Subjects
catalysis, cross-metathesis, enyne, fatty acid esters, ruthenium, Science, Organic chemistry, QD241-441
Abstract

Conjugated 1,3-dienes are important building blocks in organic and polymer chemistry. Enyne metathesis is a powerful catalytic reaction to access such structural domains. Recent advances and developments in ene–yne cross-metathesis (EYCM) leading to various compounds of interest and their intermediates, that can directly be transformed in tandem procedures, are reviewed in this article. In addition, the use of bio-resourced olefinic substrates is presented.

Published
2011
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9. C–H Bond Alkylation of Cyclic Amides with Maleimides via a Site-Selective-Determining Six-Membered Ruthenacycle

Author

Thierry Roisnel, Rafael Gramage-Doria, Marion Goujon, Christian Bruneau, Yu-Chao Yuan, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Agence Nationale de la Recherche, CA15106, European Cooperation in Science and Technology, Centre National de la Recherche Scientifique, China Scholarship Council, Université de Rennes 1, Rennes Metropole, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
C h bond, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Stereochemistry, Site selectivity, education, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Alkylation, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, A-site, chemistry, Amide, Functional group, Surface modification, Maleimide
Abstract

International audience; The first example of a ruthenium-catalyzed C–H bond alkylation via six-membered ruthenacycles is presented. This is disclosed for the C–H bond alkylation of biologically relevant cyclic amides with maleimide derivatives. The cyclic tertiary amide core acted as a directing group (DG) enabling formation of six-membered cycloruthenated species responsible for the control of the regio- and site selectivity of the reaction as well as the excellent functional group tolerance. Unexpectedly, cyclic amides were found to be better DGs than pyridine-containing ones or cyclic imides for this type of C–H bond functionalization.

Published
2019
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10. New derivatives from dehydrodieugenol B and its methyl ether displayed high anti-Trypanosoma cruzi activity and cause depolarization of the plasma membrane and collapse the mitochondrial membrane potential

Author

Thalita S. Galhardo, Anderson K. Ueno, Thaís A. Costa-Silva, André G. Tempone, Wagner A. Carvalho, Cedric Fischmeister, Christian Bruneau, Dalmo Mandelli, João Henrique G. Lago, Universidade Federal do ABC = Federal University of ABC = Université Fédérale de l'ABC [Brazil] (UFABC), Federal University of Sao Paulo (Unifesp), Instituto Adolfo Lutz [São Paulo, Brazil], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The authors acknowledge CAPES−COFECUB for support to the project no. PHC 884-17 (France) and 883/2017 (Brazil), CNPq (project 312288/2019-0 and 404843/2018-2), and FAPESP (2021/02789-7, 2021/04464-8, 2018/01258-5, 2018/07885-1, 2018/10279-6, 2017/24931-4, 2017/17044-1, and 2016/05006-5), CAPES (Finance Code 001), Institutional Internationalization Program CAPES-PrInt/UFABC and the Multi-User Central Facilities (CEM/UFABC) for the experimental support. J.H.G.L., A.G.T. and D.M. also thank CNPq for fellowships. Finally, T. S. G. thanks the CAPES−COFECUB grant 88887.198050/2018-00.

Subjects
Membrane Potential, Mitochondrial, Biological Products, Trypanosoma cruzi, Cell Membrane, General Medicine, Anisoles, Toxicology, Humans, Neolignans, [CHIM]Chemical Sciences, Calcium, Chagas Disease, Reactive Oxygen Species, Mitochondrial membrane, Plasma membrane
Abstract

International audience; In the present work, dehydrodieugenol B (1) and its methyl ether (2), isolated from Nectandra leucantha twigs, were used as starting material for the preparation of two new derivatives (1a and 2a) containing an additional methoxycarbonyl unit on allyl side chains. Compounds 1a and 2a demonstrated activity against trypomastigotes (EC(50) values of 13.5 and 23.0 μM, respectively) and against intracellular amastigotes (EC(50) values of 10.2 and 6.1 μM, respectively). Additionally, compound 2a demonstrated no mammalian cytotoxicity up to 200 μM whereas compound 1a exhibited a CC(50) value of 139.8 μM. The mechanism of action studies of compounds 1a and 2a demonstrated a significant depolarization of the plasma membrane potential in trypomastigotes, followed by a mitochondrial membrane potential collapse. Neither calcium level nor reactive oxygen species alterations were observed after a short-time incubation. Considering the potential of compound 2a against T. cruzi and its simple preparation from the natural product 2, isolated from N. leucantha, this compound could be considered a new hit for future drug design studies in Chagas disease.

Published
2022
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11. Ruthenium-catalyzed C–H bond functionalization in cascade and one-pot transformations

Author

Christian Bruneau, Rafael Gramage-Doria, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1, and Conseil National de la Recherche Scientifique

Subjects
Green chemistry, C-H bond functionalization, Tandem, 010405 organic chemistry, green chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Chemical reaction, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Ruthenium, Inorganic Chemistry, One-pot sequential reactions, Transition metal, chemistry, Cascade, Materials Chemistry, Cascade reactions, Surface modification, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Ruthenium catalysis
Abstract

International audience; Ruthenium complexes are well known as remarkable pre-catalysts for challenging C-H bond functionalizations. Combining them with other types of chemical reactions in a tandem or one-pot fashion is appealing from a sustainable point of view because it gives access to new strategies to diminish steps devoted to purification and isolation of (sometimes unstable) intermediates. This non-exhaustive review highlights the different approaches enabling these technologies with a particular focus on the understanding for the compatibility of the different reaction sequences. More precisely, ruthenium-catalyzed C-H bond functionalization turned out to be compatible with several organic transformations, metal-mediated reactions and transition metal catalysis. Graphical abstract Highlights-Ruthenium complexes are compatible with one-pot and tandem transformations involving C-H bond functionalization.-Ruthenium-catalyzed C-H bond functionalization has been successfully coupled with other C-H bond functionalization reactions.-Different organic and metal-mediated transformations operate in a concerted manner with ruthenium-catalyzed C-H bond functionalization.-The merger of ruthenium-catalyzed C-H bond functionalization strategies with several transition metal catalysis is attractive for green chemistry and sustainable approaches. Ru catalysis C-H bond functionalization metal catalysis organic reactions cascade and one-pot substrates products metal meditated

Published
2021
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12. Fluorine-containing ruthenium-based olefin metathesis catalysts

Author

Christian Bruneau, Dmitry A. Petropavlovskikh, Salekh M. Masoud, Sergey N. Osipov, Daria V. Vorobyeva, A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences [Moscow] (RAS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Peoples Friendship University of Russia [RUDN University] (RUDN), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry, Olefin metathesis, 010405 organic chemistry, chemistry.chemical_element, Organic chemistry, [CHIM]Chemical Sciences, Fluorine containing, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ruthenium, Catalysis
Abstract

The review summarizes literature data on the methods for the introduction of fluorine atoms and fluoralkyl groups into different ligands to construct metathesis-active ruthenium carbene complexes. It also analyzes the influence of fluorinated ligands on the catalytic activity of the complexes. The choice, structure and positions of fluorinated substituents in NHC ligands are generally dictated by the desire to increase the electrophilicity of the ruthenium atom due to the electron-withdrawing effect of fluorine atoms and fluoroalkyl groups, resulting, as a rule, in an increase in the activity of the ruthenium complex. In catalysts with unsymmetrical fluorine-containing NHC ligands, there is a possibility of additional Ru–F coordination, making the complexes much more stable and, consequently, more active. The presence of fluorine in chelating alkylidene ligands provides an increase in the catalyst initiation rate due to a weakening of the ruthenium – heteroatom bond. Besides, the introduction of polyfluoroalkyl groups into ligands solves the problem of catalyst recovery using fluorous biphasic systems for reuse. The bibliography includes 172 references.

Published
2021
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13. Ruthenium-catalysed oxidative coupling of vinyl derivatives and application in tandem hydrogenation

Author

Hervé Ruffin, Naba Abuhafez, Rafael Gramage-Doria, Raghu Kamaraj, Christian Bruneau, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), CNRS Centre National de la Recherche Scientifique (CNRS) European Commission, Universite de Rennes 1, ANR-JCJC French National Research Agency (ANR) [ANR-19-CE07-0039], Fondation Rennes 1, Region Bretagne Region Bretagne [1715], ANR-19-CE07-0039,REMOTCAT,Fonctionalisation 'remote' des molecules par catalyse supramoleculaire(2019), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
inorganic chemicals, Ester derivatives, Adipic acid, Tandem, 010405 organic chemistry, Chemistry, chemistry.chemical_element, Oxidative phosphorylation, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Ruthenium, chemistry.chemical_compound, Reagent, [CHIM]Chemical Sciences, Oxidative coupling of methane
Abstract

International audience; The first ruthenium-catalyzed oxidative homo- and cross-coupling of exclusive vinyl derivatives giving highly valued 1,3-diene building blocks is reported. The catalytic system is based on readily available reagents and it mainly delivers the E,E isomer. This methodology also enables the synthesis of adipic acid ester derivatives in a one-pot fashion after in situ ruthenium-catalyzed hydrogenation.

Published
2021
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14. Cross metathesis of (-)-beta-pinene, (-)-limonene and terpenoids derived from limonene with internal olefins

Author

Cédric Fischmeister, Luciana Sarmento Fernandes, Dalmo Mandelli, Christian Bruneau, Wagner Carvalho, Elsa Caytan, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Universidade Federal do ABC (UFABC), CAPES-COFECUB Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES) [88887.144564/2017-00], CNPqConselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPQ) [312288/2019-0, 404843/2018-2], FAPESP Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2018/01258-5, 2017/24931-4, 2016/05006-5, BEPE 2019/18981-4, 2015/26787-2], CAPES Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES) [001], CAPES-COFECUB (France) [PHC 884-17], CAPES-COFECUB (Brazil) Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES) [883/2017], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidade Federal do ABC = Federal University of ABC = Université Fédérale de l'ABC [Brazil] (UFABC)

Subjects
chemistry.chemical_classification, Olefin fiber, Limonene, Ruthenium catalyst, Double bond, 010405 organic chemistry, Olefin metathesis, Process Chemistry and Technology, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Metathesis, 01 natural sciences, Catalysis, 0104 chemical sciences, Ruthenium, Terpene, chemistry.chemical_compound, chemistry, Cyclic terpenes, Organic chemistry, [CHIM]Chemical Sciences, Sustainable chemistry, Dimethyl carbonate
Abstract

International audience; The straightforward functionalization of sterically demanding alpha,alpha-disubstituted double bonds of beta-pinene, (-)-limonene and (-)-limonene terpenoids has been achieved via cross metathesis with internal olefins. The reactions are catalyzed by second generation ruthenium catalysts in dimethyl carbonate as green solvent or under neat conditions. This transformation provides a clean process for the access to functionalized bulky cyclic terpenes where the terminal double bond generates a trisubstituted olefin.

Published
2021
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15. Direct Access to (+/-)-10-Desbromoarborescidine A from Tryptamine and Pentane-1,5-diol

Author

Apurba Ranjan Sahoo, V. Murugesh, Gummidi Lalitha, Surisetti Suresh, Christian Bruneau, Gangavaram V. M. Sharma, Mathieu Achard, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Council of Scientific and Industrial Research [India] (CSIR), CSIR Indian Institute of Chemical Technology (IICT), CEFIPRA/IFCPAR [5105-4], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Green chemistry, Tryptamine, 010405 organic chemistry, Chemistry, green chemistry, natural products, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Diol, Hydrogen transfer, Homogeneous catalysis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, 01 natural sciences, homogeneous catalysis, 0104 chemical sciences, 3. Good health, Pentane, chemistry.chemical_compound, indoloquinolizidine, hydrogen transfer, Organic chemistry
Abstract

International audience; A single step synthetic strategy for (+/-)10- desbromoarborescidine A is described. Starting from tryptamine and pentane-1,5-diol, this acceptorless dehydrogenative condensation process is efficiently catalyzed by a ruthenium complex featuring proton-responsive phosphine-pyridone ligand.

Published
2020
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16. Cationic versus anionic Pt complex: The performance analysis of a hybrid-capacitor, DFT calculation and electrochemical properties

Author

Thierry Roisnel, Ali Bayri, Serdar Altin, Sedat Yaşar, Christian Bruneau, E. Oz, Mitat Akkoç, S. Demirel, İsmail Özdemir, Vincent Dorcet, Inönü University, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Inönü University/Turkey / project numbers of G-2016/52, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Cyclic voltammetry, chemistry.chemical_element, Ionic bonding, 010402 general chemistry, Electrochemistry, DFT, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, Ring-expanded N-heterocyclic carbene, Materials Chemistry, Platinum ionic complex, Physical and Theoretical Chemistry, Spectroscopy, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Hybrid capacitor, Cationic polymerization, 0104 chemical sciences, chemistry, Yield (chemistry), Physical chemistry, [CHIM.OTHE]Chemical Sciences/Other, Platinum, Carbene
Abstract

The synthesis and characterization of cationic versus anionic platinum(II) complex of the type [PtCl3(DMSO)]−[NHC]+ (NHC: N-heterocyclic carbene) is reported for the first time. The complex 3 was synthesized from silver(I)-NHC 2, and K2[PtCl4] in DMSO at 80 °C under exclusion of light. The ionic platinum(II) complex was obtained in high yield and fully characterized by 1H, 13C, 195Pt NMR and HRMS spectroscopy, X-ray diffraction and elemental analysis. The structural properties of the complex were investigated by using Gaussian suit and the obtained parameters were crosschecked with the X-ray data. The HOMO-LUMO energies and electrostatic surface mapping of the complex were calculated and the results were discussed with the capacitive properties of the complex. Electrochemical analysis by cyclic voltammetry (CV) of the complex shows reversible redox peaks about platinum center. The complex was used as an electrode material for the capacitor device and result is promising that the highest performance of complex 3 was found as 10.22 F/g.

Published
2019
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17. Ruthenium(<scp>ii</scp>)-catalysed selective C(sp2)–H bond benzoxylation of biologically appealing N-arylisoindolinones

Author

Christian Bruneau, Yu-Chao Yuan, Thierry Roisnel, and Rafael Gramage-Doria

Subjects
Steric effects, chemistry.chemical_classification, 010405 organic chemistry, Hydrogen bond, Carboxylic acid, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Biochemistry, Medicinal chemistry, 0104 chemical sciences, Ruthenium, Catalysis, chemistry.chemical_compound, chemistry, Amide, Physical and Theoretical Chemistry, Selectivity
Abstract

Site- and regio-selective aromatic C–H bond benzoxylations were found to take place using biologically appealing N-arylisoindolinones under ruthenium(II) catalysis in the presence of (hetero)aromatic carboxylic acid derivatives as coupling partners. Besides the presence of two potential C(sp2)–H sites available for functionalization in the substrates, exclusive ortho selectivity was achieved in the phenyl ring attached to the nitrogen atom. Notably, the reactions occurred in a selective manner as only mono-functionalized products were formed and they tolerated a large number of functional chemical groups. The ability of the cyclic tertiary amide within the isoindolinone skeleton to act as a weak directing group in order to accommodate six-membered ring ruthenacycle intermediates appears to be the key to reach such high levels of selectivity. In contrast, the more sterically demanding cyclic imides were unreactive under identical reaction conditions.

Published
2019
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18. Merging Transition-Metal Catalysis with Phthalimides: A New Entry to Useful Building Blocks

Author

Christian Bruneau, Yu-Chao Yuan, Rafael Gramage-Doria, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Phthalimides, Primary (chemistry), 010405 organic chemistry, Chemistry, Organic Chemistry, Carbonyl reduction, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Phthalimide, chemistry.chemical_compound, Transition metal, [CHIM]Chemical Sciences, Organic synthesis, ComputingMilieux_MISCELLANEOUS
Abstract

Phthalimides have found their main application in organic synthesis as protecting groups for primary amines during the multistep synthesis of biologically relevant targets. On the other hand, phthalimide functionalization is rather challenging and it is traditionally associated with the use of over-stoichiometric amounts of environmentally hazardous reagents. In this short review, we describe and discuss how, in the last decades, transition-metal catalysts have provided useful organic building blocks after selective transformation of the phthalimide skeleton in a more efficient and sustainable manner.1 Introduction2 Partial Carbonyl Reduction3 Full Carbonyl Reduction4 Aromatic Ring Reduction5 Five-Membered-Ring Opening6 Conclusion

Published
2018
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19. Selective and Efficient Iridium Catalyst for the Reductive Amination of Levulinic Acid into Pyrrolidones

Author

Haiyun Huang, Shengdong Wang, Cédric Fischmeister, Christian Bruneau, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Hydrogen, General Chemical Engineering, chemistry.chemical_element, Homogeneous catalysis, 010402 general chemistry, 01 natural sciences, Reductive amination, Catalysis, chemistry.chemical_compound, Levulinic acid, Environmental Chemistry, Organic chemistry, General Materials Science, Iridium, Amination, heterocycles, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, amination, [CHIM.CATA]Chemical Sciences/Catalysis, iridium, homogeneous catalysis, 0104 chemical sciences, Solvent, General Energy, chemistry, biomass conversion
Abstract

International audience; The catalytic reductive amination of levulinic acid (LA) into pyrrolidones with an iridium catalyst using H2 as hydrogen source is reported. The chemoselective iridium catalyst displayed high efficiency for the synthesis of a variety of N-substituted 5-methyl-2-pyrrolidones and N-arylisoindolinones. N-Substituted 5-methyl-2-pyrrolidone was evaluated as a bio-sourced substitute solvent to NMP (N-Methyl-pyrrolidone) in the catalytic arylation of 2-phenylpyridine.

Published
2017
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20. Efficient Iridium Catalysts for Base-Free Hydrogenation of Levulinic Acid

Author

Shengdong Wang, Christian Bruneau, Vincent Dorcet, Haiyun Huang, Cédric Fischmeister, Thierry Roisnel, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), China Scholarship Council, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Formic acid, chemistry.chemical_element, levulinic acid, 010402 general chemistry, Transfer hydrogenation, 01 natural sciences, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, -valerolactone, Levulinic acid, [CHIM]Chemical Sciences, Organic chemistry, Dehydrogenation, Iridium, Physical and Theoretical Chemistry, ruthenium, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Chemistry, Ligand, Organic Chemistry, iridium, Homogeneous catalysis, Combinatorial chemistry, 0104 chemical sciences, Ruthenium, transfer hydrogenation, hydrogenation
Abstract

The synthesis and characterization of new dicationic ruthenium and iridium complexes bearing a dipyridylamine ligand (dpa) are reported. These complexes display an unusual zwitterionic molecular structure in the solid state. The iridium complex [Cp*Ir(dpa)(OSO3)] (Ir1) was found to be very efficient in base-free hydrogenation of levulinic acid into γ-valerolactone (GVL). TONs as high as 174000 in hydrogenation have been obtained. We have demonstrated that reduction of LA into GVL by transfer hydrogenation with formic acid is in fact operating by hydrogenation fed by preliminary formic acid dehydrogenation. A mechanism based on the characterization and isolation of Ir–H complexes is proposed.

Published
2017
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21. PEPPSI‐Type Palladium–NHC Complexes: Synthesis, Characterization, and Catalytic Activity in the Direct C5‐Arylation of 2‐Substituted Thiophene Derivatives with Aryl Halides

Author

İsmail Özdemir, Henri Doucet, Christian Bruneau, Murat Kaloğlu, Vincent Dorcet, Inönü University, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This work was financially supported by the Technological Scientific Research Council of Turkey TÜBİTAK-BOSPHORUS (109T605) and the İnönü University Research Fund (İ. Ü. B. A. P.: 2015/41-Güdümlü)., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Aryl, chemistry.chemical_element, Heterocycles, [CHIM.CATA]Chemical Sciences/Catalysis, Carbon-13 NMR, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, PEPPSI, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Pyridine, Carbenes, Benzimidazolium salts, Proton NMR, Molecule, Substituted thiophenes, Palladium, Alkyl
Abstract

International audience; Six benzimidazolium salts, having two nitrogen atoms substituted by various alkyl groups, have been synthesized in high yields. The benzimidazolium salts readily converted into the corresponding PEPPSI-type palladium–NHC complexes (PEPPSI = pyridine-enhanced precatalyst preparation, stabilization, and initiation). The structures of all compounds have been characterized by 1H NMR, 13C NMR, and IR spectroscopy, as well as elemental analysis techniques, which support the proposed structures. The molecular structure of one complex has been determined by single-crystal X-ray diffraction. The catalytic activity of the PEPPSI-type palladium–NHC complexes has been evaluated with respect to the direct C5-arylation of 2-substituted thiophene derivatives with various aryl halides. This arylation occurs efficiently and selectively at the C5-position of 2-substituted thiophene derivatives.

Published
2017
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22. Base-controlled product switch in the ruthenium-catalyzed protodecarbonylation of phthalimides: a mechanistic study

Author

Massimo Christian D'Alterio, Rafael Gramage-Doria, Christian Bruneau, Yu-Chao Yuan, Albert Poater, Giovanni Talarico, Dipartimento di Scienze Chimiche, University of Naples Federico II = Università degli studi di Napoli Federico II, Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona (IQCC), Universitat de Girona (UdG), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), PGC2018-097722-B-I00, Ministerio de Ciencia e Innovación, UNGI08-4E-003, European Regional Development Fund, Centre National de la Recherche Scientifique, China Scholarship Council, Agence Nationale de la Recherche, Université de Rennes 1, European Cooperation in Science and Technology, Università degli studi di Napoli Federico II, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), D'Alterio, M. C., Yuan, Y. -C., Bruneau, C., Talarico, G., Gramage-Doria, R., and Poater, A.

Subjects
Phthalimides, Reaction mechanism, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Catalysis, Transition state, 0104 chemical sciences, Phthalimide, chemistry.chemical_compound, Catalytic cycle, Polymer chemistry, Reactivity (chemistry), Chemoselectivity
Abstract

International audience; The whole reaction mechanism of the ruthenium-catalyzed protodecarbonylation of N-substituted phthalimides into secondary amides was unravelled by a combined experimental and theoretical study. The chemoselectivity of the reaction, which is catalyzed by para-cymene coordinated Ru(II) species all over the catalytic cycle, is exclusively controlled by the unique roles of the bases. Meanwhile, in the presence of K2CO3 or KOH at high temperatures, the same product (benzamide) is mainly formed, whereas at low temperatures, KOH led to an unexpected side-product (phthalamic acid) and no reactivity was observed with K2CO3. The non-covalent interactions between the potassium cations and the different carbonyl groups in the molecules are key to providing a thermodynamically favourable pathway with energetically accessible transition states. The unexpected formation of carbon dioxide (CO2) in the course of the reaction originates from the phthalimide substrate and the base K2CO3 in two different elementary steps, respectively.

Published
2020
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23. Tandem hydroformylation/isomerization/hydrogenation of bio-derived 1-arylbutadienes for the regioselective synthesis of branched aldehydes

Author

Cédric Fischmeister, Pierre H. Dixneuf, Artur V. Granato, Gabriel M. Vieira, Elena V. Gusevskaya, Christian Bruneau, Eduardo N. dos Santos, Universidade Federal de Minas Gerais [Belo Horizonte] (UFMG), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Conselho Nacional de Desenvolvimento Científico e Tecnológico, CAPES−COFECUB, INCT-Catálise, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Xantphos, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, Fragrance, Markovnikov's rule, Regioselectivity, [CHIM.CATA]Chemical Sciences/Catalysis, Conjugated system, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Organic chemistry, Hydroformylation, Tandem catalysis, Selectivity, Isomerization
Abstract

International audience; The rhodium-catalyzed hydroformylation of 1-arylbutadienes derived from lignocellulosic bio-resources has been carried out in toluene and green solvents. In the presence of DPPE and XANTPHOS ligands, a regioselective Markovnikov Rh-H insertion takes place resulting in branched aldehydes in high selectivity, which contrasts with previous results obtained from aliphatic conjugated dienes. Depending on the nature of the diphosphine ligand, conjugated enals or saturated aldehydes are obtained in good to excellent selectivity. The later have a potential interest for fragrance industry, as they are homologous to commercial fragrance ingredients.

Published
2020
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24. Transformations of bio-sourced 4-hydroxyphenylpropanoids based on olefin metathesis

Author

Naceur Hamdi, Cédric Fischmeister, Christian Bruneau, Hallouma Bilel, Université de Carthage - University of Carthage, Qassim University [Kingdom of Saudi Arabia], Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1, Centre National de la Recherche Scientifique, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Natural products, Multi-step, Olefin metathesis, 010405 organic chemistry, Chemistry, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Catalysis, Olefins, 0104 chemical sciences, Inorganic Chemistry, High yield, Organic chemistry, Phenol derivatives, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Cross metathesis
Abstract

International audience; 4-Hydroxyphenylpropanoids represent an important class of natural products directly extracted from plants or derived from lignocelullosic materials. They are phenol derivatives equipped with a terminal propenyl group, which is perfectly suited for applications involving olefin metathesis processes. In this review, we show that conditions have been found to achieve their self-metathesis, cross metathesis as well as some sequential transformations with metathesis as a key step with high yields and controlled stereoselectivities. Some applications in multi-step synthesis of biological relevant natural products involving metathetic transformations of 4-hydroxyphenylpropanoids are also reported.

Published
2020
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25. Functionalization of (-)-β-pinene and (-)-limonene via cross metathesis with symmetrical internal olefins

Author

Luciana Sarmento Fernandes, Cédric Fischmeister, Christian Bruneau, Wagner Carvalho, Dalmo Mandelli, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Universidade Federal do ABC (UFABC), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, CAPESCoordenação de Aperfeiçoamento de Pessoal de Nível Superior, CAPES, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidade Federal do ABC = Federal University of ABC = Université Fédérale de l'ABC [Brazil] (UFABC)

Subjects
chemistry.chemical_classification, Limonene, Nitrile, Double bond, 010405 organic chemistry, Process Chemistry and Technology, chemistry.chemical_element, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Metathesis, 01 natural sciences, Catalysis, 0104 chemical sciences, Ruthenium, Solvent, ruthenium catalysis, chemistry.chemical_compound, chemistry, Organic chemistry, [CHIM]Chemical Sciences, cross metathesis, Dimethyl carbonate, terpenes
Abstract

International audience; The straightforward functionalization of sterically demanding α,α-disubstituted double bonds of the natural products β-pinene and limonene via cross metathesis with symmetrical internal olefins is described. The reaction is catalyzed by Hoveyda-Grubbs type ruthenium catalysts in dimethyl carbonate as green solvent and makes possible the clean introduction of ester and nitrile groups in one step without formation of byproducts.

Published
2020
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26. Direct Access to (±)-10-Desbromoarborescidine A from Tryptamine and Pentan-1,5-diol

Author

Gangavaram V. M. Sharma, Gummidi Lalitha, Mathieu Achard, Christian Bruneau, Apurba Ranjan Sahoo, V. Murugesh, and Surisetti Suresh

Subjects
Tryptamine, chemistry.chemical_compound, chemistry, Diol, chemistry.chemical_element, Single step, Homogeneous catalysis, Carbon-13 NMR, Combinatorial chemistry, Phosphine, Ruthenium, Catalysis
Abstract

A single step synthetic strategy for (±)10- Desbromoarborescidine A is described. Starting from tryptamine and pentan-1,5-diol, this acceptorless dehydrogenative condensation process is efficiently catalyzed by a ruthenium complex featuring proton-responsive phosphine pyridone ligand.Manuscript is available supporting material is available and includes experimental procedures, characterization of compounds, 1H, 13C NMR spectra and chromatograms.

Published
2019
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27. Site-selective Ru-catalyzed C-H bond alkenylation with biologically relevant isoindolinones: a case of catalyst performance controlled by subtle stereo-electronic effects of the weak directing group

Author

Thierry Roisnel, Rafael Gramage-Doria, Christian Bruneau, Yu-Chao Yuan, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), China Scholarship Council, COST Action (CHAOS) [CA15106], CNRS, Université de Rennes 1, Rennes Métropole, Agence Nationale de la Recherche (ANR-JCJC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
010405 organic chemistry, chemistry.chemical_element, Indoprofen, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Ruthenium, chemistry.chemical_compound, chemistry, Catalytic cycle, Group (periodic table), Functional group, Electronic effect, medicine, Surface modification, [CHIM]Chemical Sciences, medicine.drug
Abstract

International audience; The first use of biologically relevant isoindolinones as weak directing groups in transition metal-catalyzed carbon-carbon bond formation via C-H bond functionalization is presented. Notably, besides the presence of two aromatic C-H sites available for functionalization, selective mono-alkenylation in the ortho-position with respect to the nitrogen atom were achieved with a readily available ruthenium catalyst. The scalability, versatility and high functional group tolerance of the catalysis enabled the late-stage functionalization of biologically relevant indoprofen and further derivatizations. Preliminary mechanistic studies indicate (1) the ease of the C-H bond activation step, (2) the key role of the carbonyl group as a weak directing group throughout the catalytic cycle and (3) the unexpected subtle differences associated between cyclic amides and imides as weak directing groups in ruthenium-catalyzed C-H bond alkenylation reactions. The isolation and role of an unprecedented off-cycle ruthenium complex is discussed as well.

Published
2019
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28. Site-Selective Ruthenium-Catalyzed C–H Bond Arylations with Boronic Acids: Exploiting Isoindolinones as a Weak Directing Group

Author

Rafael Gramage-Doria, Thierry Roisnel, Christian Bruneau, Yu-Chao Yuan, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), ANR-JCJC, Agence Nationale de la Recherche, CA15106, European Cooperation in Science and Technology, Centre National de la Recherche Scientifique, China Scholarship Council, Université de Rennes 1, Rennes Metropole, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
C h bond, 010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Catalysis, Ruthenium, chemistry, Group (periodic table), Site selective, Surface modification, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

Biologically relevant N-arylisoindolinones efficiently underwent arylation reactions under ruthenium catalysis via C–H bond functionalization. The reactions exclusively led to monoarylated products...

Published
2019
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29. Ruthenium(ii)-catalysed selective C(sp

Author

Yu-Chao, Yuan, Christian, Bruneau, Thierry, Roisnel, and Rafael, Gramage-Doria

Subjects
Nitrogen, Amides, Benzoates, Carbon, Catalysis, Ruthenium, Oxindoles
Abstract

Site- and regio-selective aromatic C-H bond benzoxylations were found to take place using biologically appealing N-arylisoindolinones under ruthenium(ii) catalysis in the presence of (hetero)aromatic carboxylic acid derivatives as coupling partners. Besides the presence of two potential C(sp

Published
2019

30. Investigation of hybrid‐capacitor properties of ruthenium complexes

Author

Sedat Yaşar, Vincent Dorcet, İsmail Özdemir, S. Altundag, Ali Bayri, Christian Bruneau, Serdar Altin, E. Oz, and Thierry Roisnel

Subjects
Capacitor, Fuel Technology, Materials science, Nuclear Energy and Engineering, Chemical engineering, chemistry, Renewable Energy, Sustainability and the Environment, law, Energy Engineering and Power Technology, chemistry.chemical_element, law.invention, Ruthenium
Published
2019
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31. Iridium Catalyzed Hydrogenation and Dehydrogenation of N-Heterocycles in Water under Mild Conditions

Author

Christian Bruneau, Cédric Fischmeister, Shengdong Wang, Haiyun Huang, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), China Scholarship Council, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
quinolines, Hydrogen, General Chemical Engineering, chemistry.chemical_element, Homogeneous catalysis, 02 engineering and technology, 010402 general chemistry, Photochemistry, Iridium, 01 natural sciences, 7. Clean energy, Reversible reaction, Catalysis, Hydrogen economy, Environmental Chemistry, General Materials Science, Dehydrogenation, business.industry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, homogeneous catalysis, 0104 chemical sciences, General Energy, hydrogenation, 0210 nano-technology, business, Stoichiometry
Abstract

International audience; An efficient catalytic method is presented for the hydrogenation of N-heterocycles. The iridium-based catalyst operates under mild conditions in water without any co-catalyst or stoichiometric additives. The catalyst also promotes the reverse reaction of dehydrogenation of N-heterocycles, hence displaying appropriate characteristics for a future hydrogen economy based on liquid organic hydrogen carriers (LOHCs).

Published
2019
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32. Ruthenium and Iridium Dipyridylamine Catalysts for the Efficient Synthesis of γ-Valerolactone by Transfer Hydrogenation of Levulinic Acid

Author

Christian Bruneau, Shengdong Wang, Thierry Roisnel, Vincent Dorcet, Cédric Fischmeister, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), China Scholarship Council, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Formic acid, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, Transfer hydrogenation, 01 natural sciences, 0104 chemical sciences, Catalysis, Turnover number, Ruthenium, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Polymer chemistry, Levulinic acid, [CHIM]Chemical Sciences, Organic chemistry, Iridium, Physical and Theoretical Chemistry, Triethylamine
Abstract

International audience; The selective and efficient transfer hydrogenation of levulinic acid into γ-valerolactone was performed with new ruthenium and iridium catalysts bearing dipyridylamine (dpa) ligands. Reactions were performed in the presence of formic acid and triethylamine using catalyst loading as low as 0.05 mol % with a ruthenium complex (turnover number = 1980). Recyclability of a ruthenium catalyst was demonstrated by running 6 consecutive reactions in almost quantitative yields.

Published
2017
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33. Nonconventional Supramolecular Self‐Assemblies of Zinc(II)–Salphen Building Blocks

Author

Rafael Gramage-Doria, Samia Kahlal, Christian Bruneau, Thierry Roisnel, Jean-Francois Halet, Thomas Groizard, Vincent Dorcet, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Absorption spectroscopy, 010405 organic chemistry, Hydrogen bond, Chemistry, Intermolecular force, Supramolecular chemistry, Infrared spectroscopy, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, symbols.namesake, Crystallography, symbols, [CHIM]Chemical Sciences, Molecule, Van der Waals radius, ComputingMilieux_MISCELLANEOUS, Natural bond orbital
Abstract

In the presence of methanol (or ethanol) and acetone molecules, a zinc(II)–salphen [salphen = N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamine] building block gives rise to discrete supramolecular dimers involving both intermolecular hydrogen bonding and unique oxygen···oxygen interactions, that is, the O···O distances are much shorter than twice the van der Waals radius of an oxygen atom. These types of unexpected self-assembled structures have been studied thoroughly through a combination of experimental (X-ray diffraction, IR spectroscopy, solid-state UV/Vis absorption spectroscopy, and elemental analysis) and theoretical [DFT and natural bond orbital (NBO) calculations] studies. However, their solution structures involve different equilibrating species according to variable-temperature 1H NMR spectroscopy. The replacement of the methanol (or ethanol) and acetone molecules by bulkier isopropyl alcohol and 2-butanone, respectively, leads to structures with no oxygen···oxygen interactions. An infinite supramolecular polymeric chain stabilized by hydrogen bonding is obtained in the presence of water. The present study highlights that even well-explored molecules can provide extremely interesting possibilities for metallo-supramolecular chemistry.

Published
2016
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34. Front Cover: Direct Access to (±)‐10‐Desbromoarborescidine A from Tryptamine and Pentane‐1,5‐diol (Asian J. Org. Chem. 6/2020)

Author

Christian Bruneau, Gummidi Lalitha, Gangavaram V. M. Sharma, Mathieu Achard, Surisetti Suresh, V. Murugesh, and Apurba Ranjan Sahoo

Subjects
Tryptamine, Green chemistry, Pentane, chemistry.chemical_compound, Front cover, chemistry, Organic Chemistry, Diol, Hydrogen transfer, Organic chemistry, Homogeneous catalysis
Published
2020
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35. Ru-Catalyzed Selective C–H Bond Hydroxylation of Cyclic Imides

Author

Christian Bruneau, Yu-Chao Yuan, Vincent Dorcet, Rafael Gramage-Doria, Thierry Roisnel, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Science des Procédés Céramiques et de Traitements de Surface (SPCTS), Université de Limoges (UNILIM)-Ecole Nationale Supérieure de Céramique Industrielle (ENSCI)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Financial support by CNRS, Universite de Rennes 1, RennesMetropole, China Scholarship Council (Ph.D. grant to Y.-C.Y.), and COST Action CA15106 (CHAOS) is acknowl-edged., Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, Substrate (chemistry), 010402 general chemistry, Ring (chemistry), 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Ruthenium, Catalysis, Hydroxylation, chemistry.chemical_compound, chemistry, Reagent, [CHIM]Chemical Sciences, Reactivity (chemistry), Palladium
Abstract

International audience; We report on cyclic imides as weak directing groups for selective monohydroxylation reactions using ruthenium catalysis. Whereas acyclic amides are known to promote the hydroxylation of the C(sp2)–H bond enabling five-membered ring ruthenacycle intermediates, the cyclic imides studied herein enabled the hydroxylation of the C(sp2)–H bond via larger six-membered ruthenacycle intermediates. Furthermore, monohydroxylated products were exclusively obtained (even in the presence of overstoichiometric amounts of reagents), which was rationalized by the difficulty to accommodate coplanar intermediates once the first hydroxyl group was introduced into the substrate. The same reactivity was observed in the presence of palladium catalysts.

Published
2019
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36. Base-free dehydrogenation of aqueous and neat formic acid with Iridium(III)Cp*(dipyridylamine) catalysts

Author

Thierry Roisnel, Shengdong Wang, Christian Bruneau, Haiyun Huang, Cédric Fischmeister, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
formic acid, Formic acid, General Chemical Engineering, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Iridium, 01 natural sciences, Catalysis, chemistry.chemical_compound, Polymer chemistry, Environmental Chemistry, General Materials Science, Dehydrogenation, ComputingMilieux_MISCELLANEOUS, Aqueous solution, Energy, Ligand, Dipyridylamine, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, 0104 chemical sciences, General Energy, chemistry, Amine gas treating, 0210 nano-technology, Carbon monoxide, Hydrogen
Abstract

The selective dehydrogenation of formic acid by iridium(III) Cp*(dipyridylamine) catalysts is reported. The electron-enriched catalyst [IrIII Cp*{(4-dimethylaminopyridin-2-yl-κΝ)(pyridin-2'-yl-κΝ)amine}(OSO3 )] gave the best performances enabling the base free dehydrogenation of aqueous and neat formic acid. In both cases the reaction was selective with no carbon monoxide detectable. The IrIII complex demonstrated latent behavior, which may be of practical utility. Experimental results suggest an outer-sphere interaction with the ligand.

Published
2019
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37. Ruthenium(II)-(Arene)-N-Heterocyclic Carbene Complexes: Efficient and Selective Catalysts for the N -Alkylation of Aromatic Amines with Alcohols

Author

Nazan Kaloğlu, İsmail Özdemir, Christian Bruneau, Mathieu Achard, Inönü University, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Borrowing hydrogen, chemistry.chemical_element, Homogeneous catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, Alkylation, Carbon-13 NMR, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Ruthenium, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, Proton NMR, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carbene
Abstract

International audience; A series of unsymmetrical 1,3-disubstituted benzimidazolium chlorides were synthesized as N-heterocyclic carbene (NHC) precursors. These compounds were used for synthesis of the new ruthenium(II) complexes of the type [RuCl2(arene)(NHC)], (arene = η 6-p-cymene). The structures of all compounds were characterized by 1 H NMR, 13 C NMR and FT-IR spectroscopy techniques. The catalytic activity of the ruthenium complexes has been evaluated with respect to the mono-N-alkylation reactions of aromatic amines with various alcohol derivatives under solvent-free conditions at 120 o C using the borrowing hydrogen strategy.

Published
2019
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38. Formic acid as a hydrogen source for the iridium-catalyzed reductive amination of levulinic acid and 2-formylbenzoic acid

Author

Shengdong Wang, Haiyun Huang, Cédric Fischmeister, Christian Bruneau, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), China Scholarship CouncilChina Scholarship Council, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Hydrogen, 010405 organic chemistry, Formic acid, Ligand, Aqueous two-phase system, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Reductive amination, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Levulinic acid, Organic chemistry, [CHIM]Chemical Sciences, Iridium, ComputingMilieux_MISCELLANEOUS
Abstract

The aqueous phase catalytic reductive amination of levulinic acid (LA) into pyrrolidones and 2-formylbenzoic acid into N-arylisoindolines is reported. The catalytic reaction involves an iridium catalyst bearing an electron-rich dipyridylamine ligand and uses formic acid as a hydrogen source. The chemoselective iridium catalyst displayed high efficiency for the synthesis of a variety of N-substituted 5-methyl-2-pyrrolidones, N-substituted 6-methyl-2-piperidinones and N-arylisoindolinones.

Published
2019
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39. 2,2'-Dipyridylamines more than just sister members of the bipyridine family. Applications and achievements in homogeneous catalysis and photoluminescent materials

Author

Christian Bruneau, Jean-Luc Renaud, Shengdong Wang, Cédric Fischmeister, Sylvain Gaillard, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Le Havre Normandie (ULH), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Photoluminescence, Denticity, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Homogeneous catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Inorganic Chemistry, Bipyridine, chemistry.chemical_compound, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

International audience; 2,2'-Dipyridylamine (dpa) and related compounds belong to the family of polydentate nitrogen ligands. More than a century has passed since its first report but new complexes and applications have been emerging in the recent years owing to the versatility of dpa-based architectures. This review aims to present and highlight the main achievements attained with dpa-containing metal complexes in the domains of homogeneous catalysis and luminescent materials.

Published
2019
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41. Cross metathesis of unsaturated epoxides for the synthesis of polyfunctional building blocks

Author

Kristýna Šichová, Antoine Dupé, Cédric Fischmeister, Meriem K. Abderrezak, Zahia Kabouche, Christian Bruneau, Nancy Dominguez-Boblett, Université frères Mentouri Constantine I (UMC), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidad de Sevilla / University of Sevilla, Université Mentouri Constantine [Algérie] (UMC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), and Universidad de Sevilla

Subjects
Diol, Organic Chemistry, Epoxide, Metathesis, Full Research Paper, 3. Good health, lcsh:QD241-441, chemistry.chemical_compound, Chemistry, chemistry, lcsh:Organic chemistry, Polymer chemistry, Alkoxy group, epoxide, Organic chemistry, Ring-opening metathesis polymerisation, [CHIM]Chemical Sciences, cross metathesis, lcsh:Q, Acrylonitrile, Methyl acrylate, tandem reactions, lcsh:Science, Acyclic diene metathesis, ruthenium catalysts
Abstract

The cross metathesis of 1,2-epoxy-5-hexene (1) with methyl acrylate and acrylonitrile was investigated as an entry to the synthesis of polyfunctional compounds. The resulting cross metathesis products were hydrogenated in a tandem fashion employing the residual ruthenium from the metathesis step as the hydrogenation catalyst. Interestingly, the epoxide ring remained unreactive toward this hydrogenation method. The saturated compound resulting from the cross metathesis of 1 with methyl acrylate was transformed by means of nucleophilic ring-opening of the epoxide to furnish a diol, an alkoxy alcohol and an amino alcohol in high yields.

Published
2015
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42. Selective Ruthenium-Catalyzed Hydrochlorination of Alkynes: One-Step Synthesis of Vinylchlorides

Author

Hubert Klein, Christian Bruneau, Sylvie Dérien, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CNRS, Ministère de la recherche, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
[SDV]Life Sciences [q-bio], Markovnikov's rule, Alkyne, chemistry.chemical_element, alkynes, 010402 general chemistry, Hydrohalogenation, 01 natural sciences, Catalysis, Atom economy, Organic chemistry, ruthenium, chemistry.chemical_classification, alkenes, 010405 organic chemistry, Alkene, General Chemistry, General Medicine, Combinatorial chemistry, 0104 chemical sciences, Ruthenium, Syn and anti addition, chemistry, synthetic methods, hydrohalogenation
Abstract

International audience; An unprecedented ruthenium-catalyzed direct and selective alkyne hydrochlorination is reported and leads to vinylchlorides in excellent yields with atom economy. The reaction proceeds at room temperature from terminal alkynes and provides a variety of chloroalkenes. Only the regioisomer resulting from the formal Markovnikov addition is selectively formed. Mechanistic studies show the stereoselective syn addition of HCl to alkynes at room temperature and suggest a chloro hydrido Ru(IV) species as a key intermediate of the reaction.

Published
2015
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43. N-Alkylation and N,C-Dialkylation of Amines with Alcohols in the Presence of Ruthenium Catalysts with Chelating N-Heterocyclic Carbene Ligands

Author

Orhan Büyükgüngör, Christian Bruneau, Onur Şahin, Zeynel Şahin, Nevin Gürbüz, İsmail Özdemir, Mathieu Achard, and Ondokuz Mayıs Üniversitesi

Subjects
Primary (chemistry), Organic Chemistry, Acetal, chemistry.chemical_element, Nuclear magnetic resonance spectroscopy, Alkylation, Medicinal chemistry, Catalysis, Ruthenium, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Organic chemistry, Chelation, Physical and Theoretical Chemistry, Carbene
Abstract

ACHARD, Mathieu/0000-0003-0578-9680; bruneau, christian/0000-0002-2220-1458; Sahin, Onur/0000-0003-3765-3235 WOS: 000356841800031 A series of new benzimidazolium salts and ruthenium(II) complexes containing chelating N-heterocyclic carbenes (NHCs) functionalized with a benzylic group and an acetal group were prepared. All of the synthesized compounds were characterized by elemental analysis and NMR spectroscopy, and the molecular structures of 2c and 2d were determined by X-ray crystallography. All of the,complexes were tested in the alkylation of cyclic amine derivatives with alcohols and showed excellent activity in this reaction. Cyclic amines were alkylated with primary and heteroaromatic alcohols. The Ru-NHC Complexes also catalyzed N,C3-dialkylation of cyclic amines. Technological and Scientific Research Council of Turkey (TUBITAK)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [112T303]; Inonu University Research FundInonu University [I.U. B.A.P: 2014/Gudumlu-53] This work was financially supported by the Technological and Scientific Research Council of Turkey (TUBITAK) (112T303) and the Inonu University Research Fund (I.U. B.A.P: 2014/Gudumlu-53).

Published
2015
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44. Cross metathesis of bio-sourced fatty nitriles with acrylonitrile

Author

Cédric Fischmeister, Christian Bruneau, Jean-Luc Couturier, Jean-Luc Dubois, Johan Bidange, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Arkema, Colombes, Centre de recherche Rhône-Alpes (CRRA), Arkema (Arkema), The research leading to these results has received funding from the European Union Seventh Framework Programme (FP7/2007‐2013) under grant agreement n° 241718 EuroBioRef., Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
chemistry.chemical_classification, ω-Dinitriles, Nitrile, Double bond, Chemistry, α, Diethyl carbonate, chemistry.chemical_element, General Chemistry, Homogeneous catalysis, Metathesis, 3. Good health, Ruthenium, chemistry.chemical_compound, Green chemistry, [CHIM]Chemical Sciences, Organic chemistry, Ring-opening metathesis polymerisation, Renewables, Acrylonitrile, Ruthenium catalysis, Acyclic diene metathesis
Abstract

International audience; We report the cross metathesis of two olefinic partners contg. different types of nitrile functionality. Thus, cross metathesis of fatty nitriles with acrylonitrile have been achieved with olefin metathesis ruthenium catalysts. 10-Undecenenitrile provides 2-dodecenedinitrile with a high turnover no. of 13,280 in the green solvent, di-Et carbonate. Cross metathesis with the internal carbon-carbon double bond of oleonitrile gave the expected products, and the cleavage of the internal double bond proved to be more difficult probably owing to faster catalyst decomposition.

Published
2015
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45. Olefin metathesis transformations in thermomorphic multicomponent solvent systems

Author

Cédric Fischmeister, Hallouma Bilel, Fethy Zagrouba, Shilin Huang, Naceur Hamdi, Christian Bruneau, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Carthage - University of Carthage, The authors are grateful to the French–Tunisian joint project PHC-UTIQUE no. 09G1203 for the financial support to HB. We acknowledge B. Lefeuvre (OMC, Multifunctional Inorganic Materials) for ICP measurements., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Olefin metathesis, Process Chemistry and Technology, chemistry.chemical_element, Homogeneous catalysis, General Chemistry, Thermomorphic solvent system, Ruthenium, Catalysis, Solvent, chemistry.chemical_compound, chemistry, Propylene carbonate, [CHIM]Chemical Sciences, Ring-opening metathesis polymerisation, Organic chemistry, Renewables, Acrylonitrile, Methyl acrylate, ComputingMilieux_MISCELLANEOUS
Abstract

Homogeneous catalysis is a major actor of modern chemistry with a growing impact on clean and sustainable chemical processes. However, for many industrial applications of homogeneously catalyzed reactions, an easy separation and recovery of the catalyst should be guaranteed. Temperature-dependent multicomponent solvent (TMS) systems have been evaluated in ruthenium catalyzed olefin metathesis transformations. Propylene carbonate was found a suitable solvent for the ruthenium catalyzed ring-closing and cross-metathesis transformations of a variety of substrates including renewable fatty esters. The potential of a TMS system consisting of propylene carbonate/ethyl acetate/cyclohexane was then evaluated in the cross-metathesis of the renewable methyl 10-undecenoate with methyl acrylate and acrylonitrile.

Published
2015
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46. New fluorinated catalysts for olefin metathesis

Author

Salekh M. Masoud, Artur K. Mailyan, Alexander S. Peregudov, Sergey N. Osipov, Christian Bruneau, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Olefin metathesis, 010405 organic chemistry, Ligand, Chemistry, General Chemistry, 010402 general chemistry, Metathesis, 01 natural sciences, 0104 chemical sciences, 3. Good health, Catalysis, Ring-closing metathesis, [CHIM]Chemical Sciences, Ring-opening metathesis polymerisation, Organic chemistry, ComputingMilieux_MISCELLANEOUS, Acyclic diene metathesis
Abstract

New olefin metathesis catalysts, analogues of Grubbs II ones, bearing hexafluoroisopropylmethoxy groups in NHC ligand, provide high conversions in model ring closing metathesis of diallylmalonate and cross metathesis of allylbenzene with 1,3-diacetoxybut-2-ene.

Published
2016
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47. Synthesis of N-heterocyclic carbene-palladium-PEPPSI complexes and their catalytic activity in the direct C-H bond activation

Author

Murat Kaloğlu, Nazan Kaloğlu, Muhammad Tahir, Pierre H. Dixneuf, Cengiz Arıcı, Henri Doucet, İsmail Özdemir, Christian Bruneau, Bekir Çetinkaya, Inönü University, University of Sargodha, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Ege University (EGE), 109T605, B.A.P. 2015/41, Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Ege University ( EGE ), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Infrared spectroscopy, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, [ CHIM.CATA ] Chemical Sciences/Catalysis, pyrroles, Materials Chemistry, Molecule, Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Pyrrole, 010405 organic chemistry, Aryl, Organic Chemistry, direct arylation, [ CHIM.COOR ] Chemical Sciences/Coordination chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 3. Good health, 0104 chemical sciences, PEPPSI, chemistry, Benzimidazolium salts, Carbene, N-heterocyclic carbene, PEPPSI-type palladium-NHC complexes, Palladium
Abstract

A series of benzimidazolium salts having their two nitrogen atoms substituted by bulky groups have been synthesized. The benzimidazolium salts were readily converted into the corresponding palladium-NHC-PEPPSI complexes with general formula [PdBr2(NHC) (Py)], (NHC = N-heterocyclic carbene; PEPPSI = pyridine-enhanced precatalyst preparation, stabilisation, and initiation). The structures of all new compounds were characterized by NMR, IR spectroscopy and microanalysis techniques, which support the proposed structures. The molecular structure of complex 2g was determined by singlecrystal X-ray diffraction study. Next, the palladium-NHC-PEPPSI complexes were used as catalysts in the direct C5-arylation of 1-methylpyrrole-2-carboxaldehyde by aryl halides. These complexes exhibited moderate to high catalytic activities and gave C-H activation selectively at the C5-position of 1methylpyrrole- 2-carboxaldehyde. Both electron-donating and electron-withdrawing substituents were well tolerated with catalytic systems based on these complexes, even non-activated aryl chlorides such as chlorobenzene or 4-chlorotoluene were coupled with pyrrole in moderate yields. (C) 2017 Elsevier B.V. All rights reserved.

Published
2018
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48. Ruthenium(II)-Catalyzed C–H (Hetero)Arylation of Alkenylic 1, n -Diazines ( n = 2, 3, and 4): Scope, Mechanism, and Application in Tandem Hydrogenations

Author

Thierry Roisnel, Sylvain Achelle, Françoise Robin-le Guen, Rafael Gramage-Doria, Christian Bruneau, Vincent Dorcet, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), CA15106, European Cooperation in Science and Technology, Centre National de la Recherche Scientifique, Université de Rennes 1, Rennes M?tropole, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
C-H acti- vation, Tandem, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, chemistry.chemical_element, Ruthenium catalyst, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Reductive elimination, 0104 chemical sciences, Catalysis, Ruthenium, chemistry, cross-coupling, Product formation, diazines, hydrogenation, ruthenium, Lone pair, Isomerization
Abstract

International audience; A general ruthenium(II)-catalyzed methodology enabling the (hetero)arylation of alkenylic C-H bonds utilizing a series of synthetically appealing diazines as directing groups is presented. Despite the presence of additional nitrogen lone pairs remote from the C-H bond activation site, which could eventually poison the catalyst, the reaction times are short (3 hours), thus being suitable for selective double C-H bond arylation. Mixtures of E:Z isomeric products were observed in some cases, which were further hydrogenated in a tandem manner in the presence of the remaining ruthenium catalyst from the first step; representing an alternative approach to more difficult C(sp 3)-H bond functionalization. According to mechanistic studies, the unexpected E:Z product formation seems to occur by thermal C=C bond isomerization after the reduc-tive elimination step.

Published
2018
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49. Investigation Of Potential Hybrid Capacitor Property Of Chelated N-Heterocyclic Carbene Ruthenium(Ii) Complex

Author

E. Oz, Thierry Roisnel, Vincent Dorcet, Serdar Altin, Mitat Akkoç, Sedat Yaşar, İsmail Özdemir, Ali Bayri, Christian Bruneau, S. Demirel, Inönü University, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 114Z036, TÜBITAK, Türkiye Bilimsel ve Teknolojik Araştirma Kurumu, G2016/52, 2006K-120470, 2016/53, Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
chemistry.chemical_element, 010402 general chemistry, Electrochemistry, Transfer hydrogenation, 01 natural sciences, Biochemistry, [ CHIM ] Chemical Sciences, Ruthenium, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, Polymer chemistry, Hybrid capasitor, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Cyclic Voltametry of ruthenium(II), ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Aryl, Organic Chemistry, Nuclear magnetic resonance spectroscopy, 0104 chemical sciences, Chelate ligand, chemistry, Cyclic voltammetry, Carbene, N-heterocyclic carbene
Abstract

The synthesis of chelated ruthenium(II) complex type Ru(eta(6)-HMB) (NHC) Cl (NHC = N-heterocyclic carbene, HMB = hexamethylbenzene) is presented. The ruthenium(II)-NHC complex 6 was obtained in good yield and was fully characterised by NMR spectroscopy, X-ray diffraction and HRMS analysis. Electrochemical analysis by cyclic voltammetry (CV) revealed reversible redox behaviour at the ruthenium centre in 6. DFT studies and the catalytic activity of complex 6 on transfer hydrogenation reaction of aryl ketones are also presented. The potential hybrid capacitor applications of Ru-NHC complex is discussed and reported firstly in the literature. It was found that the highest performance was found at 20.1 F/g, which is a promising result for energy storage applications. (c) 2018 Elsevier B.V. All rights reserved.

Published
2018
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50. Transformations of terpenes and terpenoids via carbon-carbon double bond metathesis

Author

Luciana Sarmento Fernandes, Pierre H. Dixneuf, Cédric Fischmeister, Christian Bruneau, Wagner Carvalho, Eduardo N. dos Santos, Dalmo Mandelli, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Universidade Federal do ABC (UFABC), Federal University of Minas Gerais (UFMG), CAPES-COFECUB [PHC 884-17, 883/2017], CNPq [422290/2016-5, 485545/2013-6], FAPESP [2015/26787-2], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidade Federal do ABC = Federal University of ABC = Université Fédérale de l'ABC [Brazil] (UFABC), and Universidade Federal de Minas Gerais = Federal University of Minas Gerais [Belo Horizonte, Brazil] (UFMG)

Subjects
chemistry.chemical_classification, Ethenolysis, Double bond, 010405 organic chemistry, Alkene, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Ring (chemistry), Metathesis, 01 natural sciences, 7. Clean energy, Catalysis, 0104 chemical sciences, Terpene, chemistry.chemical_compound, Ring-closing metathesis, chemistry, 13. Climate action, Organic chemistry, Isoprene
Abstract

International audience; Stimulated by the strong interest in replacing fossil raw materials by renewable feedstocks in chemical industry, alkene metathesis of unsaturated bio-sourced olefins has been recently investigated with the objective of producing high-value molecules using green and atom economic strategies. It is due time to review what has been achieved in this field using terpenes and terpenoids as olefin metathesis partners. These substrates, derived from the isoprene structure, present different types of carbon-carbon double bonds that can be involved in self metathesis, ring closing metathesis, cross metathesis including ethenolysis, and ring opening metathesis. The successful achievements and remaining bottlenecks in this field will be discussed.

Published
2018
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