Bingwei Zhou, Yuanyuan Hu, and Congyang Wang*

Grignard-type C−H nucleophilic addition to aldehydes and nitrles is a severe challenge for inert C−H bonds. Herein, a manganese-catalyzed nucleophilic addition of inert C(sp²)−H bonds to aldehydes and nitriles is disclosed by virtue of a dual activation strategy, namely, merging C−H activation by a manganese catalyst and aldehyde/nitrile activation by zinc bromide. The reactions feature mild reaction conditions, excellent regio- and stereoselectivity, and wide substrate scopes including both aromatic and olefinic C−H bonds and being applicable to a large variety of aldehydes and nitriles. Moreover, mechanistic studies shed light on possible catalytic cycles.

This work has been published in Angew. Chem. Int. Ed., 2015, 54, 13659–13663.