Synthesis and metathesis reactions of a phosphine-free dihydroimidazole carbene ruthenium complex

Gessler, Simon; Randl, Stefan; Blechert, Siegfried

doi:10.1016/s0040-4039(00)01808-6

Cited by 506 publications

(242 citation statements)

References 13 publications

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“…Motif A is the classical Grubbs precatalysts where L 2 is mostly either PCy 3 [4] or H 2 IMes [7], while in Motif D, a hetero-atom like sulfur [14] is typically introduced in the alkylidene ligand of these precatalysts. Hoveyda et al [15][16][17][18] synthesized precatalysts with Motif B that showed exceptional stability that allowed its use in reagent-grade solvents and/or in air [15], while this motif was also used by Van der Schaaf et al [14] for the fine-tuning of gel times for the better handling of ROMP (ring-opening metathesis polymerization) in technical processes. In Motif C, where X is oxygen, the chelating ligand competes in both initiation and coordination with the incoming alkene substrate for a vacant coordination site [17].…”

Section: Synthesis Of Pyridinyl Alcoholsmentioning

confidence: 99%

“…Hoveyda et al [15][16][17][18] synthesized precatalysts with Motif B that showed exceptional stability that allowed its use in reagent-grade solvents and/or in air [15], while this motif was also used by Van der Schaaf et al [14] for the fine-tuning of gel times for the better handling of ROMP (ring-opening metathesis polymerization) in technical processes. In Motif C, where X is oxygen, the chelating ligand competes in both initiation and coordination with the incoming alkene substrate for a vacant coordination site [17]. The synthesis of this design concept was first achieved by Grubbs et al [19] and later by Verpoort et al [20,21].…”

Section: Synthesis Of Pyridinyl Alcoholsmentioning

confidence: 99%

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Synthesis and Application of Novel Ruthenium Catalysts for High Temperature Alkene Metathesis

et al. 2017

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Four pyridinyl alcohols and the corresponding hemilabile pyridinyl alcoholato ruthenium carbene complexes of the Grubbs second generation-type RuCl(H 2 IMes)(OˆN)(=CHPh), where,1-phenyl methanolato and 1-(2 -pyridinyl)-1-(2 -methoxyphenyl),1-phenyl methanolato, are synthesized in very good yields. At high temperatures, the precatalysts showed high stability, selectivity and activity in 1-octene metathesis compared to the Grubbs first and second generation precatalysts. The 2-/4-chloro-and 4-methoxy-substituted pyridinyl alcoholato ligand-containing ruthenium precatalysts showed high performance in the 1-octene metathesis reaction in the range 80-110 • C. The hemilabile 4-methoxy-substituted pyridinyl alcoholato ligand improved the catalyst stability, activity and selectivity for 1-octene metathesis significantly at 110 • C.

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Section: Synthesis Of Pyridinyl Alcoholsmentioning

confidence: 99%

Section: Synthesis Of Pyridinyl Alcoholsmentioning

confidence: 99%

Synthesis and Application of Novel Ruthenium Catalysts for High Temperature Alkene Metathesis

et al. 2017

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“…The first example of cross-metathesis of terminal olefins with acrylonitrile was described with the Schrock catalyst Mo(=CHCMe 2 Ph)(NAr)(OCMe(CF 3 ) 2 ), Ar = 2,6-diisopropylphenyl, affording moderate yields [45]. Then ruthenium catalysts, especially containing a heterocyclic carbene ligand, improved the cross-metathesis of acrylonitrile with terminal alkenes [46][47][48][49][50], with an example of internal alkene in the presence of copper salt [51].…”

Section: Cross-metathesis Of Acrylonitrile With Unsaturated Acids or 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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“…In fact, the Hoveyda complex 3 is also a chelated carbene, but it is stable and initiates by dissociation of the chelated ether. [42,43] Alternatively, chelation may result in carbene decomposition. This would be far more problematic, yet decomposition occurring via chelates in the second generation carbene has not been directly observed.…”

Section: Tandem Metathesis-mentioning

confidence: 99%

“…Alkyne insertion is the first step in enyne metathesis, and stopping the reaction at the vinyl carbene stage is a challenge. Successful syntheses have taken a clue from the design of the Hoveyda complex [42,43] which features a chelated carbene fragment. Chelation imposes kinetic stability to the vinyl carbene intermediate.…”

Section: By Alkyne Insertion Into a Metalmentioning

confidence: 99%

Ruthenium vinyl carbene intermediates in enyne metathesis

Diver

2007

Coordination Chemistry Reviews

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This review provides an overview of ruthenium vinyl carbene reactivity as it relates to enyne metathesis. Methods for the synthesis of metathesis-active and metathesis-inactive complexes are also summarized. Some of the early hypotheses about vinyl carbene intermediates in enyne metatheses were tested in the arena of synthetic chemistry and subsequently led to mechanistic studies. In these two areas, studies from the author's labs are described. There are still many unresolved questions in enyne metathesis that trace back to vinyl carbene reactivity. Hopefully this review will stimulate further investigation into vinyl carbene reactivity which should further refine our understanding of catalytic enyne metathesis.

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Synthesis and metathesis reactions of a phosphine-free dihydroimidazole carbene ruthenium complex

Cited by 506 publications

References 13 publications

Synthesis and Application of Novel Ruthenium Catalysts for High Temperature Alkene Metathesis

Synthesis and Application of Novel Ruthenium Catalysts for High Temperature Alkene Metathesis

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

Ruthenium vinyl carbene intermediates in enyne metathesis

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