Ruthenium–Benzylidenes and Ruthenium–Indenylidenes as Efficient Catalysts for the Hydrogenation of Aliphatic Nitriles into Primary Amines

Miao, Xiaowei; Bidange, Johan; Dixneuf, Pierre H.; Fischmeister, Cédric; Bruneau, Christian; Dubois, Jean‐Luc; Couturier, Jean‐Luc

doi:10.1002/cctc.201200511

Cited by 47 publications

(27 citation statements)

References 99 publications

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“…provided the saturated C12 a,x-amino ester 18, which was isolated in 89% yield [69] (Scheme 9). The presence of t BuOK not only created the hydrogenation catalyst but was shown to inhibit the formation of secondary amines.…”

Section: Selective Hydrogenation Of Nitrile Esters With Ruthenium Alkmentioning

confidence: 99%

“…6). The catalytic hydrogenation of nitrile ester 20 using 3 mol% of catalyst IV under an initial hydrogen pressure of 20 bar at 80°C for 40 h in the presence of 30 mol% of t BuOK, led to complete conversion of compound 20 and 75% of compound 18 and 22% of compound 16 were obtained [69] (Scheme 9). The hydrogenation of 20 with ruthenium catalysts I, II, and VIII-X (3 mol%) in the presence of 30 mol% of t BuOK provided excellent yields of amino ester 18, except for catalyst I.…”

Section: Selective Hydrogenation Of Nitrile Esters With Ruthenium Alkmentioning

confidence: 99%

“…The hydrogenation of 20 with ruthenium catalysts I, II, and VIII-X (3 mol%) in the presence of 30 mol% of t BuOK provided excellent yields of amino ester 18, except for catalyst I. On lowering the catalyst loading to 1 mol%, and on shortening the reaction time to 16 h, ruthenium catalysts II and X offered the best efficiency for the production of 18 from nitrile ester 20 [69] (Scheme 9).…”

Section: Selective Hydrogenation Of Nitrile Esters With Ruthenium Alkmentioning

confidence: 99%

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Alkene Metathesis Catalysis: A Key for Transformations of Unsaturated Plant Oils and Renewable Derivatives

Dixneuf

Bruneau

Fischmeister

2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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-This account presents the importance of ruthenium-catalysed alkene cross-metathesis for the catalytic transformations of biomass derivatives into useful intermediates, especially those developed by the authors in the Rennes (France) catalysis team in cooperation with chemical industry. The cross-metathesis of a variety of functional alkenes arising from plant oils, with acrylonitrile and fumaronitrile and followed by catalytic tandem hydrogenation, will be shown to afford linear amino acid derivatives, the precursors of polyamides. The exploration of crossmetathesis of bio-sourced unsaturated nitriles with acrylate with further catalytic hydrogenation has led to offer an excellent route to a,x-amino acid derivatives. That of fatty aldehydes has led to bifunctional long chain aldehydes and saturated diols. Two ways of access to functional dienes by ruthenium-catalyzed ene-yne cross-metathesis of plant oil alkene derivatives with alkynes and by cross-metathesis of bio-sourced alkenes with allylic chloride followed by catalytic dehydrohalogenation, are reported. Ricinoleate derivatives offer a direct access to chiral dihydropyrans and tetrahydropyrans via ring closing metathesis. Cross-metathesis giving value to terpenes and eugenol for the straightforward synthesis of artificial terpenes and functional eugenol derivatives without C=C bond isomerization are described.Résumé -Catalyse de métathèse d'oléfines : une clé pour des transformations d'huiles végétales insaturées et de substances renouvelables -Cet article présente l'importance de la réaction de métathèse croisée des oléfines par catalyse au ruthénium pour la transformation de dérivés de la biomasse en produits utiles pour l'industrie. Il constitue une revue des principaux travaux réalisés dans ce domaine par les auteurs dans leur équipe de catalyse à Rennes (France) en coopération avec l'industrie chimique. La métathèse croisée d'une variété d'oléfines fonctionnelles issues des huiles végétales avec l'acrylonitrile et le fumaronitrile, suivie d'une hydrogénation tandem conduit à des dérivés d'amino acides linéaires, précurseurs de polyamides par polycondensation. L'exploration de la métathèse croisée de nitriles insaturés bio-sourcés avec des acrylates a conduit à des dérivés d'a,x-amino acides, tandis que les aldéhydes gras ont permis un accès rapide à des aldéhydes bifonctionnalisés à longue chaîne et à des diols saturés. Deux voies d'accès à des diènes conjugués fonctionnels impliquant des réactions de métathèse catalysées par le ruthénium à partir d'oléfines issues de la biomasse sont décrites : l'une par métathèse croisée avec un alcyne, l'autre par métathèse croisée avec un chlorure allylique suivie Dedicated to the memory of Yves Chauvin, a great and inspiring pioneer in organometallic catalysis

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Section: Selective Hydrogenation Of Nitrile Esters With Ruthenium Alkmentioning

confidence: 99%

Section: Selective Hydrogenation Of Nitrile Esters With Ruthenium Alkmentioning

confidence: 99%

Section: Selective Hydrogenation Of Nitrile Esters With Ruthenium Alkmentioning

confidence: 99%

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Alkene Metathesis Catalysis: A Key for Transformations of Unsaturated Plant Oils and Renewable Derivatives

Dixneuf

Bruneau

Fischmeister

2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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“…Indenylidene-ruthenium catalysts are now commonly used in catalysis based on their efficiency and the easiness of preparation from simple propargylic alcohols rather than from diazoalkanes [72,73]. Moreover the Rennes allenylidene-and indenylidene-ruthenium catalysts led us to develop many applications in alkene metathesis [100][101][102][103] some of them in cooperation with IFP [103][104][105] and Arkema [106,107] companies, and this topic is still a strong research topic in Rennes.…”

Section: Concluding Remarkmentioning

confidence: 99%

Early Steps of Homogeneous Catalysis in Rennes: Carbon Dioxide Incorporation, Alkyne Activation and Ruthenium Catalysis

Dixneuf

2014

Catal Lett

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This review reports the first discoveries in homogeneous catalysis in Rennes. Ruthenium(II) catalysts are shown to promote the activation of terminal alkynes and the synthesis of vinylcarbamates on addition of CO 2 and amines. The ruthenium-vinylidene are the key catalytic species. Applications to the addition of carboxylic acids to alkynes have opened the access to various enolesters and dienylesters via controlled catalyzed Markovnikov or anti-Markonikov additions. The catalytic synthesis of a-methylene cyclic carbonates and oxazolidinones from propargylic alcohols and CO 2 is presented and shown to lead to allene derivatives via palladium catalysis. Cp*RuX(COD) catalyst promote the head to tail oxidative couplings of alkene with alkyne, and the synthesis of functional dienes via 1,4 addition of H-nucleophiles to the biscarbene-ruthenium intermediate arising from head to head couplings of alkynes, whereas Cp*RuL 2 ? catalysts favour activation of alkynes via vinylidene intermediate.

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“…In addition, in academia a variety of transition metals including Co, Ni, Au 18 , Cu, Rh, Pd and Pt have been immobilized on different supports (C, TiO 2 , SiO 4 , Al 2 O 3 and so on) and were investigated, too [19][20][21][22][23][24][25] . On the other hand, homogeneous catalysts for the hydrogenation of nitriles are almost limited to the presence of precious metals such as Ir 26 , Rh 27 , Re 28 and Ru [29][30][31][32][33][34] .…”

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confidence: 99%

Mild and selective hydrogenation of aromatic and aliphatic (di)nitriles with a well-defined iron pincer complex

et al. 2014

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The catalytic hydrogenation of carboxylic acid derivatives represents an atom-efficient and clean reduction methodology in organic chemistry. More specifically, the selective hydrogenation of nitriles offers the possibility for a green synthesis of valuable primary amines. So far, this transformation lacks of useful, broadly applicable non-noble metal-based catalyst systems. In the present study, we describe a molecular-defined iron complex, which allows for the hydrogenation of aryl, alkyl, heterocyclic nitriles and dinitriles. By using an iron PNP pincer complex, we achieve very good functional group tolerance. Ester, ether, acetamido as well as amino substituents are not reduced in the presence of nitriles. Moreover, nitriles including an α,β-unsaturated double bond and halogenated derivatives are well tolerated in this reaction. Notably, our complex constitutes the first example of an homogeneous catalyst, which permits the selective hydrogenation of industrially important adipodinitrile to 1,6-hexamethylenediamine.

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Ruthenium–Benzylidenes and Ruthenium–Indenylidenes as Efficient Catalysts for the Hydrogenation of Aliphatic Nitriles into Primary Amines

Cited by 47 publications

References 99 publications

Alkene Metathesis Catalysis: A Key for Transformations of Unsaturated Plant Oils and Renewable Derivatives

Alkene Metathesis Catalysis: A Key for Transformations of Unsaturated Plant Oils and Renewable Derivatives

Early Steps of Homogeneous Catalysis in Rennes: Carbon Dioxide Incorporation, Alkyne Activation and Ruthenium Catalysis

Mild and selective hydrogenation of aromatic and aliphatic (di)nitriles with a well-defined iron pincer complex

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