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

McGrath, Dominic V. and Grubbs, Robert H. (1994) The mechanism of aqueous ruthenium(II)-catalyzed olefin isomerization. Organometallics, 13 (1). pp. 224-235. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20180521-133722840

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/om00013a035DOIArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
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.
Funders:
Funding AgencyGrant Number
Caltech Consortium in Chemistry and Chemical EngineeringUNSPECIFIED
Department of EducationUNSPECIFIED
NSFUNSPECIFIED
Rohm and Haas CompanyUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arnold and Mabel Beckman Laboratories of Chemical Synthesis8653
Issue or Number:1
Record Number:CaltechAUTHORS:20180521-133722840
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180521-133722840
Official Citation:The mechanism of aqueous ruthenium(II)-catalyzed olefin isomerization Dominic V. McGrath and Robert H. Grubbs Organometallics 1994 13 (1), 224-235 DOI: 10.1021/om00013a035
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86507
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:21 May 2018 20:48
Last Modified:03 Oct 2019 19:44

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