Catalytic Enantioselective Methylene C(sp3)-H Hydroxylation Using a Chiral Manganese Complex/Carboxylic Acid System.

Achieving direct C-H hydroxylation in a highly diastereo- and enantioselective manner is still a challenging goal. This reaction is mainly hindered by the potential for overoxidation of the generated alcohols as well as low stereoselectivity. Herein, we present an enantioselective benzylic C-H hydroxylation catalyzed by a manganese complex, H2O2, and a carboxylic acid in 2,2,2-trifluoroethanol. The benzylic alcohols were successfully furnished in excellent diastereoselectivities (up to >95:5) and enantioselectivities (up to 95% ee). As a highlight of this work, high diastereoselectivity of C-H hydroxylation could be achieved by tuning the amount of carboxylic acid additive.