Ligand-modulated palladium oxidation catalysis: mechanistic insights into aerobic alcohol oxidation with the Pd(OAc)(2)/pyridine catalyst system

Bradley A Steinhoff; Shannon S Stahl

doi:10.1021/ol026988e

Ligand-modulated palladium oxidation catalysis: mechanistic insights into aerobic alcohol oxidation with the Pd(OAc)(2)/pyridine catalyst system

Org Lett. 2002 Nov 14;4(23):4179-81. doi: 10.1021/ol026988e.

Authors

Bradley A Steinhoff¹, Shannon S Stahl

Affiliation

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

PMID: 12423116
DOI: 10.1021/ol026988e

Abstract

Pd(OAc)(2):pyridine (1:4) is an efficient catalyst system for the oxidation of alcohols with molecular oxygen. A mechanistic study of this reaction reveals that pyridine promotes the aerobic oxidation of palladium(0) but inhibits the oxidation of alcohol by palladium(II). Kinetic results reveal that turnover-limiting substrate oxidation consists of (i) formation of a palladium(II)-alkoxide, (ii) pyridine dissociation, and (iii) beta-hydride elimination. These results provide a framework for the design and/or screening of more effective aerobic oxidation catalysts.