Mechanism of the ruthenium-catalyzed reconstitutive condensation of allylic alcohols and terminal alkynes

Trost, Barry M.; Kulawiec, Robert J.

doi:10.1021/ja00040a015

Cited by 125 publications

(50 citation statements)

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“…In addition, the dissociation of both one PPh 3 and Cl Ϫ from 1 has been previously proposed by Trost to account for the catalytic activity of this complex in other organic transformations. [19] Finally, we found appreciable amounts of free imine in the reaction mixtures, unlike previous observations in which the imine is formed at the metal centre, by condensation between coordinated amine and aldehyde, and then, without decoordination, immediately hydrogenated to the corresponding amine. [1,5,8,11,12] …”

Section: Nmr Measurements and Mechanistic Insightscontrasting

confidence: 91%

Cyclopentadienyl Ru^II Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol

et al. 2004

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The ruthenium(II) half-sandwich complex [RuCl(η 5 -C 5 H 5 )(PPh 3 ) 2 ] (1) catalyses the reaction between methanol and alkylamines RNH 2 or R 1 R 2 NH to afford RN(CH 3 ) 2 and R 1 R 2 NCH 3 products, respectively. The reaction is quantitative and generally fast, at the methanol reflux temperature, for a wide spectrum of substrates. Starting from primary amines, the stepwise formation of RN=CH 2 , RNHCH 3 , and

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Section: Nmr Measurements and Mechanistic Insightscontrasting

confidence: 91%

Cyclopentadienyl Ru^II Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol

et al. 2004

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“…First B. M. Trost showed that using the CpRu(PPh 3 ) 2 Cl/NH 4 PF 6 catalytic system, the addition of allylic alcohols to terminal alkynes was possible and took place affording b,c-unsaturated ketones, via addition of allyl alcohol to the vinylidene intermediate and C-O bond cleavage and allyl migration (Eq. 14) [74][75][76][77].…”

Section: ð12þmentioning

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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“…[30] Loss of chloride ion from the ruthenium complex is expected to lead to the active cationic catalyst I. Vinylidene formation with alkyne 40 leads to II. Coordination of olefin 41, with loss of phosphine, can lead to III, and subsequent nucleophilic attack by the pendant alcohol can give IV.…”

Section: Intramolecularmentioning

confidence: 99%

Metal Vinylidenes as Catalytic Species in Organic Reactions

Trost

McClory

2008

Chemistry An Asian Journal

189

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Organic vinylidene species have found limited use in organic synthesis due to their inaccessibility. In contrast, metal vinylidenes are much more stable, and may be readily accessed through transition metal activation of terminal alkynes. These electrophilic species may be trapped by a number of nucleophiles. Additionally, metal vinylidenes can participate in pericyclic reactions and processes involving migration of a metal ligand to the vinylidene species. This review addresses the reactions and applications of metal vinylidenes in organic synthesis.

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Mechanism of the ruthenium-catalyzed reconstitutive condensation of allylic alcohols and terminal alkynes

Cited by 125 publications

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Cyclopentadienyl Ru^II Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol

Cyclopentadienyl Ru^II Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol

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

Metal Vinylidenes as Catalytic Species in Organic Reactions

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Mechanism of the ruthenium-catalyzed reconstitutive condensation of allylic alcohols and terminal alkynes

Cited by 125 publications

References 0 publications

Cyclopentadienyl RuII Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol

Cyclopentadienyl RuII Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol

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

Metal Vinylidenes as Catalytic Species in Organic Reactions

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Product

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Cyclopentadienyl Ru^II Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol

Cyclopentadienyl Ru^II Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol