Enantioselective alcohol oxidation reactions catalyzed by unspecific peroxygenases.

The enantioselective oxidation of alcohols can be achieved via kinetic resolution of racemic alcohols or the desymmetriza-tion 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 dis-tinct enantioselective biocatalytic alcohol oxidation approaches: UPO-catalyzed oxidation of meso-diols via desymmetriza-tion, the chemoselective oxidation of non-benzylic 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 demon-strated on a preparative scale.