A Photoenzymatic System for Alcohol Oxidation

Abstract A photocatalytic regeneration approach for the oxidized nicotinamide cofactors NAD(P)+ is presented. By simple irradiation with visible light, the rate of flavin‐mediated NAD(P)H oxidation is accelerated by two orders of magnitude. Catalytic use of the flavin is straightforward under aerobic conditions. Combined with alcohol dehydrogenases, photoenzymatic oxidation schemes are obtained allowing for selective, O2‐driven oxidation of primary and secondary alcohols. The simplicity and practical applicability of this oxidation approach is demonstrated in the oxidative lactonization of 1,4‐ and 1,5‐diols. Under nonoptimized conditions, total turnover numbers of 170 and 340 are achieved for the nicotinamide cofactor and the flavin catalyst, respectively.