Dual biocatalytic one-pot deracemization of aryl-ring-containing secondary alcohols via sequential oxidation–reduction

We report a one-pot two-step deracemization strategy for aryl-ring-containing secondary alcohols using a dual biocatalytic system that combines an unspecific peroxygenase and an alcohol dehydrogenase. In this approach, unspecific peroxygenase from Agrocybe aegerita (AaeUPO) catalyzes the non-stereoselective oxidation of secondary alcohols to their corresponding ketones. The resulting ketones are subsequently subjected to enantioselective reduction using the secondary alcohol dehydrogenase from Thermoanaerobacter pseudoethanolicus (TeSADH), affording optically active alcohols with high conversion and enantiomeric excesses of up to 99%. By selecting appropriate TeSADH mutants, the system enables the independent, highly enantioselective synthesis of either alcohol enantiomer. Notably, the AaeUPO-catalyzed oxidation proceeds without external cofactors and generates water as the sole byproduct. This work establishes a useful biocatalytic platform for the asymmetric synthesis of enantiopure alcohols.