Palladium(II)-Catalyzed Oxidation of Alcohols to Aldehydes and Ketones by Molecular Oxygen

Abstract
A novel combination of Pd(OAc)2/pyridine/MS3A catalyzes the aerobic oxidation in toluene of a variety of primary and secondary alcohols into the corresponding aldehydes and ketones in high yields. Various substituents and protecting groups are compatible with this oxidation. The ca. 2:3 ratio of O2 uptake to product yield is observed, whereas in the absence of MS3A, the ratio is ca. 1:1, suggesting the in situ formation of H2O2 and its decomposition by MS3A into water and oxygen. A catalytic cycle including the formation of a Pd(II)-alcoholate followed by β-elimination of a Pd(II)H species and a carbonyl compound and then the formation of a Pd(II)OOH species is proposed.

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