Microwave-Accelerated Ruthenium-Catalyzed Olefin Metathesis

Mayo, Kelly G.; Nearhoof, Eliza H.; Kiddle, James J.

doi:10.1021/ol025789s

Cited by 148 publications

(68 citation statements)

References 14 publications

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“…After each cycle, the volatile product was directly isolated in high yield by rapid distillation under reduced pressure. [43] The concept of performing microwave synthesis in roomtemperature ionic liquids has been applied to 1,3-dipolar cycloaddition reactions, [47] catalytic transfer hydrogenations, [48] ring-closing metathesis, [49] and the conversion of alcohols into alkyl halides. [50] As an alternative to the use of the rather expensive ionic liquids as solvents, several research groups have used ionic liquids as "doping agents" for microwave heating of otherwise nonpolar solvents such as hexane, toluene, THF, or dioxane.…”

Section: Heck Reactionsmentioning

confidence: 99%

“…With microwaves, otherwise sluggish RCM protocols have been reported to be completed within minutes or even seconds. [49,55,71,[125][126][127][128] In 2003, for example, Efskind and Undheim reported the domino RCM of dienyne 14 with a Grubbs type II catalyst (Scheme 16). [127] While the thermal process (toluene, 85 8C) required multiple addition of fresh catalyst (3 10 mol %) over a period of 9 h to furnish a 92 % yield of product 15, microwave irradiation for 10 min at 160 8C (5 mol % catalyst, toluene) led to full conversion.…”

Section: Other Transition-metal-mediated Processesmentioning

confidence: 99%

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Controlled Microwave Heating in Modern Organic Synthesis

2004

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Although fire is now rarely used in synthetic chemistry, it was not until Robert Bunsen invented the burner in 1855 that the energy from this heat source could be applied to a reaction vessel in a focused manner. The Bunsen burner was later superseded by the isomantle, oil bath, or hot plate as a source for applying heat to a chemical reaction. In the past few years, heating and driving chemical reactions by microwave energy has been an increasingly popular theme in the scientific community. This nonclassical heating technique is slowly moving from a laboratory curiosity to an established technique that is heavily used in both academia and industry. The efficiency of “microwave flash heating” in dramatically reducing reaction times (from days and hours to minutes and seconds) is just one of the many advantages. This Review highlights recent applications of controlled microwave heating in modern organic synthesis, and discusses some of the underlying phenomena and issues involved.

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Section: Heck Reactionsmentioning

confidence: 99%

Section: Other Transition-metal-mediated Processesmentioning

confidence: 99%

Controlled Microwave Heating in Modern Organic Synthesis

2004

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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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“…The next year, however, Jahngen (4) , who was one of the authors, conducted the same experiments and concluded that the rate of hydrolysis solely depends on the temperature and not on the method of heating. Mayo et al (5) conducted ring-closing metathesis reactions using microwaves and reported that microwaves accelerated the reaction. However, after that, Garbacia et al (6) conducted the same reaction both by microwave heating and conventional oil-bath heating and reported that they did not find any evidence for a significant non-thermal microwave effect.…”

Section: Introductionmentioning

confidence: 99%

Isothermal Reactor for Continuous Flow Microwave-Assisted Chemical Reaction

Matsuzawa

Togashi

Hasebe

2012

JTST

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An isothermal reactor in which reaction solutions can be controlled at constant temperature under constant microwave irradiation was developed. This is useful for investigating microwave effects on chemical reactions that are not observed under conventional heating conditions. We devised a structure in which a heat-transfer medium with a low dielectric loss factor, which hardly absorbs any microwaves, flowed outside a spiral reaction tube and designed the basic structure of the reactor using electromagnetic simulation to optimize the energy absorption rate. The conditions for increasing the temperature controlling ability of the reactor were also investigated theoretically and experimentally by taking into consideration the influences of three elements: the velocity of the internal fluid, the material for the tube, and the velocity of the external fluid. The velocity of the external fluid had the greatest influence on temperature controlling ability and the material for the tube had the least influence under the experimental conditions. The overall heat transfer coefficient was about 3.9×10 2 W/(m 2 ·K) when water flowed through the quartz reaction tube at 7.1 mm/s and the external fluid flowed outside the tube at 44 mm/s. We also tested and confirmed that the temperature of water used as internal fluid could be controlled to within ±1.5 K at 309.3 K when microwaves at 26 W were irradiated into the reactor, whereas the temperature of water was over 373 K and boiled without the heat-transfer medium flowing outside the reaction tube using a conventional method of microwave heating. In addition, we investigated microwave effects on Suzuki-Miyaura coupling reaction using the developed isothermal reactor and we confirmed that the temperatures were controlled well in the reactor. The yields obtained by microwave heating were almost the same as that obtained by oil-bath heating.

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Microwave-Accelerated Ruthenium-Catalyzed Olefin Metathesis

Cited by 148 publications

References 14 publications

Controlled Microwave Heating in Modern Organic Synthesis

Controlled Microwave Heating in Modern Organic Synthesis

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

Isothermal Reactor for Continuous Flow Microwave-Assisted Chemical Reaction

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