Mild and Selective Cobalt-Catalyzed Chemodivergent Transfer Hydrogenation of Nitriles

Herein, we describe a selective cobalt‐catalyzed chemodivergent transfer hydrogenation of nitriles to synthesize primary, secondary, and tertiary amines. The solvent effect plays a key role for the selectivity control. The general applicability of this procedure was highlighted by the synthesis of more than 70 amine products bearing various functional groups in high chemoselectivity. Moreover, this mild system achieved >2000 TONs (turnover numbers) for the transfer hydrogenation of nitriles. Selectivity is under control: A cobalt‐catalyzed chemodivergent transfer hydrogenation of nitriles for the selective synthesis of primary, secondary, and even tertiary amines has been developed. This mild system achieved >2000 TONs and more than 70 amines were produced by this strategy, highlighting the efficiency and broad applicability of this cobalt catalysis system.