Tuning Regioselectivity of Wacker Oxidation in One Catalytic System: Small Change Makes Big Step.

A regioselectivity switchable aerobic Wacker-Tsuji oxidation has been developed using catalytic tert-butyl nitrite as a simple organic redox cocatalyst. By solely switching the solvent, either substituted aldehydes or ketones could be prepared under mild aerobic conditions in good yields, respectively. A mechanistic explanation for the selectivity control is proposed.