Enantioselective Alcohol Oxidation Reactions Catalyzed by Unspecific Peroxygenases

The enantioselective oxidation of alcohols can be achieved via kinetic resolution of racemic alcohols or the desymmetrization of meso-diols. Biocatalytic alcohol oxidation approaches are known, using alcohol dehydrogenases and copper-and flavin-dependent oxidases, but the application of unspecific peroxygenases (UPOs) to enantioselective alcohol oxidation has received very little attention. As part of ongoing research into the catalytic promiscuity of UPOs, we present three distinct enantioselective biocatalytic alcohol oxidation approaches: the UPO-catalyzed oxidation of meso-diols via desymmetrization, the chemoselective oxidation of nonbenzylic sites in unsymmetrical diols, and the kinetic resolution of axially chiral biaryl alcohols. In each of the three reaction classes, the isolation of enantiomerically enriched oxidized products is demonstrated on a preparative scale.