Enantioselective Synthesis of Tertiary Alcohols by the Desymmetrizing Benzoylation of 2‐Substituted Glycerols

Complementary catalysts have been found for the enantioselective desymmetrization of 2-substituted glycerols by monobenzoylation with benzoyl chloride and Et3N to give chiral tertiary alcohols with 80 to 94 % ee (see Scheme; Bn=benzyl, Bz=benzoyl). The dibenzylbisoxazoline–CuCl2 complex 1 is remarkably effective for substrates with an alkyl substituent in the 2-position, the iminooxazoline–CuCl2 complex 2 for those with vinyl, phenyl, and benzyl substituents.