Cross‐metathesis of methyl 10‐undecenoate with diethyl maleate: Formation of an α,ω‐diester <i>via</i> a metathesis reaction network

Behr, Arno; Gomes, Jessica Pérez; Bayrak, Zeynep

doi:10.1002/ejlt.201000299

Cited by 31 publications

(11 citation statements)

References 29 publications

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“…In some examples it was shown that acrylonitrile inhibits the ruthenium-catalysed cross-metathesis of functional alkenes, whereas methyl acrylate does not inhibit this reaction as some cross-metathesis can be performed in bulk in methyl acrylate [16,17,[70][71][72]. Thus, it appeared that the linear amino ester 18 could also arise from the cross-metathesis of the 10-undecenenitrile 21 with methyl acrylate followed by hydrogenation.…”

Section: Cross-metathesis Of Renewable 10-undecenenitrile and Methyl mentioning

confidence: 99%

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: Cross-metathesis Of Renewable 10-undecenenitrile and Methyl mentioning

confidence: 99%

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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“…At the same period, this group also investigated the cross metathesis of methyl 10-undecenoate 72 (arising from the pyrolysis of castor oil) with diethyl maleate 73 leading to the diester 74 (Scheme 25). [117] Experimental parameters as well as various ruthenium-based catalysts were investigated. Again, the best results were obtained with a high catalyst loading (4 mol%) of the indenylidene catalyst Ru21 and the formation of the self-metathesis product of 72 could not be reduced below 25%.…”

Section: Cross Metathesis With Functional Olefinsmentioning

confidence: 99%

Alkene Metathesis for Transformations of Renewables

Bruneau

Fischmeister

2018

Organometallics for Green Catalysis

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“…Diethyl maleate as a co‐substrate affords the corresponding C12‐diester in high yields of 91% under optimized reaction conditions. The reaction is carried out at 70°C with 4 mol% of the catalyst Neolyst M2 for 3 h in toluene at a molar substrate ratio of 1:6 in favor of diethyl maleate . The cross‐metathesis with dimethyl maleate is even more active, yielding almost quantitative yields for dimethyl 2‐dodecenoate in only 1 h at 80°C in toluene with a substrate ratio of 1:5 and a low catalyst loading of only 0.75% Neolyst M2 .…”

Section: Metathesismentioning

confidence: 99%

The mission of addition and fission – catalytic functionalization of oleochemicals

Seidensticker

Vorholt

Behr

2015

Euro J Lipid Sci & Tech

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Oleochemicals are used in the chemical industry in numerous processes and applications, having the largest share among all other renewable resources. Besides the well‐known transformations performed at the carboxylic moiety of the alkyl chain, many natural occurring fatty compounds offer a further opportunity for refinement, that is: catalytic functionalization of the CC double bond. In the present review, the authors describe the mission of the scientific work that is performed at the chair of Technical Chemistry at the TU Dortmund towards selective and atom economic functionalization of oleochemicals. Special emphasis lays on homogenous transition metal catalysis towards potential applications of the resulting products and their continuous production in miniplant scale. The given examples are discussed in the context of the work of other groups and summarize recent developments in the field of addition and fission reactions of oleochemicals. The Mission of Addition and Fission—The functionalization of oleochemicals using homogeneous transition metal catalysis is a very elegant way for producing valuable chemicals via many possible pathways. In this review, recent contributions to e.g. addition or cleavage reactions by Behr's group at the TU Dortmund are presented and discussed in the context of relevant literature, highlighting their significance in this important field of oleochemistry.

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Cross‐metathesis of methyl 10‐undecenoate with diethyl maleate: Formation of an α,ω‐diester via a metathesis reaction network

Cited by 31 publications

References 29 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

Alkene Metathesis for Transformations of Renewables

The mission of addition and fission – catalytic functionalization of oleochemicals

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