Mechanistic study of alcohol oxidation by the Pd(OAc)(2)/O(2)/DMSO catalyst system and implications for the development of improved aerobic oxidation catalysts

Bradley A Steinhoff; Shannon R Fix; Shannon S Stahl

doi:10.1021/ja016806w

Mechanistic study of alcohol oxidation by the Pd(OAc)(2)/O(2)/DMSO catalyst system and implications for the development of improved aerobic oxidation catalysts

J Am Chem Soc. 2002 Feb 6;124(5):766-7. doi: 10.1021/ja016806w.

Authors

Bradley A Steinhoff¹, Shannon R Fix, Shannon S Stahl

Affiliation

¹ Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.

PMID: 11817948
DOI: 10.1021/ja016806w

Abstract

The Pd(OAc)2/O2/DMSO catalyst system displays impressive versatility in the aerobic oxidation of organic substrates, ranging from alcohols to olefins. This report details mechanistic insights into these reactions. Dimethyl sulfoxide (DMSO) plays no redox role in the chemistry, and kinetic experiments identify the turnover-limiting step as DMSO-promoted oxidation of palladium(0) by molecular oxygen. The "chemical oxidase" pathway characterized for this catalyst system holds great promise for the design of new aerobic oxidation reactions.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.
Research Support, U.S. Gov't, P.H.S.

MeSH terms

Alcohols / chemistry*
Catalysis
Dimethyl Sulfoxide / chemistry
Kinetics
Oxidation-Reduction
Oxygen / chemistry*
Palladium / chemistry*

Substances

Alcohols
Palladium
Oxygen
Dimethyl Sulfoxide