ChemInform Abstract: Regioselective Isomerization of 2,3‐Disubstituted Epoxides to Ketones: An Alternative to the Wacker Oxidation of Internal Alkenes.

Abstract

We report an alternative pathway to the Wacker oxidation of internal olefins involving epoxidation of trans-alkenes followed by a mild and highly regioselective isomerization to give the major ketone isomers in 66–98% yield. Preliminary kinetics and isotope labeling studies suggest epoxide ring opening as the turnover limiting step in our proposed mechanism. A similar catalytic system was applied to the kinetic resolution of select trans-epoxides to give synthetically useful selectivity factors of 17–23 for benzyl-substituted substrates.