The Mechanism of Aqueous Ruthenium(II)-Catalyzed Olefin Isomerization

Dominic V. McGrath; Robert H. Grubbs

doi:10.1021/om00013a035

The Mechanism of Aqueous Ruthenium(II)-Catalyzed Olefin Isomerization

Dominic V. McGrath, Robert H. Grubbs

Research output: Contribution to journal › Article › peer-review

192 Scopus citations

Abstract

Olefin isomerization of allylic ethers and alcohols is catalyzed by Ru^II(H₂O)₆(tos)₂ (tos = p-toluenesulfonate) (1) under mild conditions in aqueous solution to yield the corresponding carbonyl compounds. Non-allylic olefins are also isomerized, although homoallylic alcohols exhibit stability toward isomerization. An exclusive 1,3-hydrogen shift is observed in the isomerization of allyl-1,1-d₂ alcohol to propionaldehyde-1.3-d₂ and allyl-1,1-d₂ methyl ether to 1-propenyl-1,3-d₂ methyl ether by 1 in aqueous solution. The presence of crossover products from the isomerizations of mixtures of (a) allyl-3-¹³C alcohol and allyl-1,1-d₂ alcohol and (b) allyl-1,1 -d₂ methyl ether and allyl ethyl ether demonstrates that the isomerization of both alcohols and ethers occurs via intermolecular hydrogen shifts. A modified metal hydride additionelimination mechanism involving exclusive Markovnikov addition to the double bond directed by the oxygen functionality of the substrate has been proposed.

Original language	English (US)
Pages (from-to)	224-235
Number of pages	12
Journal	Organometallics
Volume	13
Issue number	1
DOIs	https://doi.org/10.1021/om00013a035
State	Published - Jan 1 1994
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "The Mechanism of Aqueous Ruthenium(II)-Catalyzed Olefin Isomerization",

abstract = "Olefin isomerization of allylic ethers and alcohols is catalyzed by RuII(H2O)6(tos)2 (tos = p-toluenesulfonate) (1) under mild conditions in aqueous solution to yield the corresponding carbonyl compounds. Non-allylic olefins are also isomerized, although homoallylic alcohols exhibit stability toward isomerization. An exclusive 1,3-hydrogen shift is observed in the isomerization of allyl-1,1-d2 alcohol to propionaldehyde-1.3-d2 and allyl-1,1-d2 methyl ether to 1-propenyl-1,3-d2 methyl ether by 1 in aqueous solution. The presence of crossover products from the isomerizations of mixtures of (a) allyl-3-13C alcohol and allyl-1,1-d2 alcohol and (b) allyl-1,1 -d2 methyl ether and allyl ethyl ether demonstrates that the isomerization of both alcohols and ethers occurs via intermolecular hydrogen shifts. A modified metal hydride additionelimination mechanism involving exclusive Markovnikov addition to the double bond directed by the oxygen functionality of the substrate has been proposed.",

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year = "1994",

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N2 - Olefin isomerization of allylic ethers and alcohols is catalyzed by RuII(H2O)6(tos)2 (tos = p-toluenesulfonate) (1) under mild conditions in aqueous solution to yield the corresponding carbonyl compounds. Non-allylic olefins are also isomerized, although homoallylic alcohols exhibit stability toward isomerization. An exclusive 1,3-hydrogen shift is observed in the isomerization of allyl-1,1-d2 alcohol to propionaldehyde-1.3-d2 and allyl-1,1-d2 methyl ether to 1-propenyl-1,3-d2 methyl ether by 1 in aqueous solution. The presence of crossover products from the isomerizations of mixtures of (a) allyl-3-13C alcohol and allyl-1,1-d2 alcohol and (b) allyl-1,1 -d2 methyl ether and allyl ethyl ether demonstrates that the isomerization of both alcohols and ethers occurs via intermolecular hydrogen shifts. A modified metal hydride additionelimination mechanism involving exclusive Markovnikov addition to the double bond directed by the oxygen functionality of the substrate has been proposed.

AB - Olefin isomerization of allylic ethers and alcohols is catalyzed by RuII(H2O)6(tos)2 (tos = p-toluenesulfonate) (1) under mild conditions in aqueous solution to yield the corresponding carbonyl compounds. Non-allylic olefins are also isomerized, although homoallylic alcohols exhibit stability toward isomerization. An exclusive 1,3-hydrogen shift is observed in the isomerization of allyl-1,1-d2 alcohol to propionaldehyde-1.3-d2 and allyl-1,1-d2 methyl ether to 1-propenyl-1,3-d2 methyl ether by 1 in aqueous solution. The presence of crossover products from the isomerizations of mixtures of (a) allyl-3-13C alcohol and allyl-1,1-d2 alcohol and (b) allyl-1,1 -d2 methyl ether and allyl ethyl ether demonstrates that the isomerization of both alcohols and ethers occurs via intermolecular hydrogen shifts. A modified metal hydride additionelimination mechanism involving exclusive Markovnikov addition to the double bond directed by the oxygen functionality of the substrate has been proposed.

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The Mechanism of Aqueous Ruthenium(II)-Catalyzed Olefin Isomerization

Abstract

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