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

Dominic V. McGrath, Robert H. Grubbs

Research output: Contribution to journalArticle

175 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)224-235
Number of pages12
JournalOrganometallics
Volume13
Issue number1
DOIs
StatePublished - Jan 1 1994
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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