CaltechAUTHORS
Published January 1994 | Version public
Journal Article Metadata-only

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

Creators

Abstract

Olefin isomerization of allylic ethers and alcohols is catalyzed by Ru^(II)(H_2O) (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 d_2 alcohol to propionaldehyde-1,3-d_2 and allyl-1,1-d_2 methyl ether to 1-propenyl-1,3-d_2 methyl ether by 1 in aqueous solution. The presence of crossover products from the isomerizations of mixtures of (a) allyl-3-^(13)C alcohol and allyl-1,1-d_2 alcohol and (b) allyl-1 ,1-d_2 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.

Additional Information

© 1994 American Chemical Society. Received October 25, 1999. This work was supported by the Caltech Consortium in Chemistry and Chemical Engineering (founding members: E. I. DuPont de Nemours & Co., Eastman Kodak Co., and the Minnesota Mining and Manufacturing Co.), the NSF, and Rohm & Haas. D.V.M. is the recipient of a Department of Education predoctoral fellowship, for which he is grateful. The authors wish to thankDr. PadBernhard for advice regarding the synthesis of Ru^(II)(H_2O)_6(tos)_2, Dr. Richard Kondrat for mass spectrometry assistance, and Prof. John Bercaw and Dr. David Wheeler for helpful discussions. We are particularly indebted to Prof. Robert J. Kulawiec for a critical reading of the manuscript and, for many helpful suggestions.

Additional details

Identifiers

Eprint ID
86507
Resolver ID
CaltechAUTHORS:20180521-133722840

Funding

Caltech Consortium in Chemistry and Chemical Engineering
Department of Education
NSF
Rohm and Haas Company

Dates

Created
2018-05-21
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Updated
2021-11-15
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Caltech Custom Metadata

Other Numbering System Name
Arnold and Mabel Beckman Laboratories of Chemical Synthesis
Other Numbering System Identifier
8653