Redox Deracemization of Tertiary Stereocenters Adjacent to an Electron-Withdrawing Group

A one-pot redox deracemization of tertiary stereocenters adjacent to an electron-withdrawing group has been reported. By using a sequential redox process consisting of DDQ-catalyzed MnO2 oxidation and asymmetric transfer hydrogenation, efficient deracemization proceeded with high levels of chemo- and enantioselectivities, enabling asymmetric access to tertiary stereocenters bearing diverse electron-withdrawing groups including perfluoroalkyl, cyano, and ester moieties, which are otherwise difficult to synthesize.