Ruthenium-Catalyzed Olefin Metathesis in Ionic Liquids

Buijsman, Rogier C.; Vuuren, and Elizabeth van; Sterrenburg, Jan Gerard

doi:10.1021/ol016769d

Cited by 141 publications

(70 citation statements)

References 13 publications

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“…Ionic Liquids (IL) as solvents have shown their ability to favour several catalytic processes [28][29][30][31][32] and alkene metathesis can be performed in Room Temperature Ionic Liquids (RTIL) since 1995 [33][34][35][36][37][38][39][40][41]. We have shown the efficient ethenolysis of methyl oleate 1 under mild conditions with several ruthenium alkylidene catalysts in organic solvents and, for the first time, in imidazolium-type ionic liquids at room temperature without C=C bond isomerization [42].…”

Section: Ethenolysis Of Methyl Oleate In Ionic Liquid For Terminal Almentioning

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: Ethenolysis Of Methyl Oleate In Ionic Liquid For Terminal Almentioning

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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“…[34] Therefore, 0.02 mol % (1.22 × 10 À3 mol L À1 octene) catalyst (1) precursor concentration was chosen since the corresponding amount of catalyst can be weighed out without introducing too large an error, while giving reasonably good turnover frequencies. Previous investigations have used this catalyst precursor at much higher concentrations; e.g., Buijsman et al [8] found that 5 mol % catalyst precursor leads to optimal results in a ringclosing metathesis. In addition, we noted that a biphasic reaction mixture resulted when 1-octene was added to any of the ionic liquids discussed here, while a homogeneous reaction mixture is formed with organic solvents (vide infra) or in solvent-free modus.…”

Section: Preliminary 1-octene Metathesis Study Using 1 As Catalyst Prmentioning

confidence: 99%

“…[6] Grubbs 1 st and 2 nd generation, and ruthenium allenylidene catalyst precursors have been investigated in detail in ring-closing metathesis. [7][8][9][10][11][12][13][14][15][16][17] Many of these reactions feature high selectivities and high reaction rates in the first run, which then decrease upon recycling due to catalyst leaching or deactivation. However, attachment of an "ionic liquid tag" to catalyst ligands hugely improves the recyclability of the system.…”

Section: Introductionmentioning

confidence: 99%

Metathesis of 1‐Octene in Ionic Liquids and Other Solvents: Effects of Substrate Solubility, Solvent Polarity and Impurities

et al. 2006

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Abstract:With the self-metathesis of 1-octene to 7-tetradecene catalyzed by Grubbs 1 st generation [benzylidene-bis(tricyclohexylphosphine)dichlororuthenium, (1)] precursor at low concentrations (0.02 mol %) as basis, the effects of the solubility of the substrate in ionic liquids, the solvent polarity, as well as the influence of various impurities stemming from the preparation of ionic liquids have been investigated. The solubility of the substrate in the ionic liquid has little effect on the conversion, and the reaction is not mass-transfer limited. While a higher polarity of an organic solvent increases the rate, it is independent of the polarity excerted by the cation of an ionic liquid. Of paramount importance for reproducible results is the purity of ionic liquids. An extensive study shows that catalyst deactivation by impurities increases in the order of water < halide < 1-methylimidazole. In the presence of water or 1-methylimidazole impurities, the Grubbs-Hoveyda precursor (3) is superior to both the 1 st (1) and 2 nd (2) generation Grubbs complexes. Under impurity-free conditions or in the presence of chloride, the performance of 2 is equivalent to that of 3.

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“…The efficiency of supported catalysts remained almost constant upto six recycles and further there is significant decrease (Table II) which may be due to either decomposition of the catalyst in the reaction media or their extraction to the organic solvent during product isolation. [24] The product selectivity for epoxide remained unaffected on using recycled catalysts, which was an indication for the structural stability of iron complex on polymer support as confirmed by comparing IR spectra of recycled catalysts with IR spectra of freshly prepared catalysts. The rate of trans-Stilbene conversion was 4.27 × 10 -7 mole dm -3 s -1 in the presence of polymer-supported iron Schiff base complex.…”

Section: Resultsmentioning

confidence: 77%

Polymer Supported Schiff Base Iron Complex for Epoxidation of Trans-stilbene

Nath¹,

Pradhan²,

Maharana³

et al. 2017

IJCEA

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Abstract-In the present investigation, the novel recyclable polystyrene anchored iron complex supported by -ONN Schiff base is synthesized. This polymer anchored iron complex is prepared by the reactions of metal solution with one molar equivalent of polystrene supported Schiff-base ligands in methanol under nitrogen atmosphere. In contrast with other polymer-supported catalysts, the greatest advantage of this catalyst system was that the cost of the catalyst was remarkably low and recycled up to six times, due to the easily accessible materials and the simple synthetic route. The higher efficiency of complexation of metal ions on the polymer anchored Schiff base than unsupported analogue was another advantages of this catalyst system. The structural study reveal that iron(III) complex is octahedral in geometry.The catalytic activities of polystyrene supported iron complex toward the epoxidation of trans-Stilbene is investigated. Experimental results indicate that the reactivity of iron complex is dramatically affected by the polymer support and the rate of trans-Stilbene conversion was 4.27 × 10 -7 moledm -3 s -1 and obeys first order kinetics. The efficiency of supported catalysts remained almost constant upto six recycles.

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Ruthenium-Catalyzed Olefin Metathesis in Ionic Liquids

Cited by 141 publications

References 13 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

Metathesis of 1‐Octene in Ionic Liquids and Other Solvents: Effects of Substrate Solubility, Solvent Polarity and Impurities

Polymer Supported Schiff Base Iron Complex for Epoxidation of Trans-stilbene

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