Site- and Enantioselective Manganese-Catalyzed Benzylic C-H Azidation of Indolines.

A manganese-catalyzed highly site- and enantioselective benzylic C-H azidation of indolines has been described. The practical method is applicable for azidation of a tertiary benzylic C-H bond with good functional group tolerance, allowing facile access to structurally diverse tertiary azide-containing indolines in high efficiency with excellent site-, chemo-, and enantioselectivity. The generality of the method was further demonstrated by site- and enantioselective azidation of the secondary benzylic C-H bond for a range of secondary azide-containing indolines. The benzylic C-H azidation method allows to straightforwardly and enantioselectively install a variety of nitrogen-based functional groups and diverse bioactive molecules at the C 3 position of indoline frameworks through post-azidation manipulations. Gram-scale synthesis was also demonstrated, further highlighting the synthetic potential of the method. Mechanistic studies by combined experiments and computations elucidated the reaction mechanism and origins of stereoselectivity.