The mechanism of aqueous ruthenium(II)-catalyzed olefin isomerization

Dominic V Mcgrath, Robert H. Grubbs

Research output: Contribution to journalArticle

173 Citations (Scopus)

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 addition-elimination 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
StatePublished - 1994
Externally publishedYes

Fingerprint

Ruthenium
Alkenes
Isomerization
isomerization
ruthenium
alkenes
ethers
alcohols
Methyl Ethers
Alcohols
Ethers
Hydrogen
Carbonyl compounds
aqueous solutions
carbonyl compounds
metal hydrides
Hydrides
Ether
shift
hydrogen

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

The mechanism of aqueous ruthenium(II)-catalyzed olefin isomerization. / Mcgrath, Dominic V; Grubbs, Robert H.

In: Organometallics, Vol. 13, No. 1, 1994, p. 224-235.

Research output: Contribution to journalArticle

@article{596d178bbbca4ff380fb417fa4b04343,
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 addition-elimination mechanism involving exclusive Markovnikov addition to the double bond directed by the oxygen functionality of the substrate has been proposed.",
author = "Mcgrath, {Dominic V} and Grubbs, {Robert H.}",
year = "1994",
language = "English (US)",
volume = "13",
pages = "224--235",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "1",

}

TY - JOUR

T1 - The mechanism of aqueous ruthenium(II)-catalyzed olefin isomerization

AU - Mcgrath, Dominic V

AU - Grubbs, Robert H.

PY - 1994

Y1 - 1994

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 addition-elimination 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 addition-elimination mechanism involving exclusive Markovnikov addition to the double bond directed by the oxygen functionality of the substrate has been proposed.

UR - http://www.scopus.com/inward/record.url?scp=0000164101&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000164101&partnerID=8YFLogxK

M3 - Article

VL - 13

SP - 224

EP - 235

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 1

ER -