Nickel-Catalyzed Chemo- and Enantioselective Hydrogenation and Deuteration of α,β-Unsaturated Ketimines Using Alcohols: Synthesis of Deuterated Chiral Allylic Amines

A nickel-catalyzed chemoselective asymmetric transfer hydrogenation of alpha,beta-unsaturated ketimines using ethanol as a hydrogen donor under mild conditions that avoid using high-pressure hydrogen gas was developed. With this catalyst, C1-selective deuterated chiral allylic amines were efficiently synthesized using only stoichiometric 2-propanol-d 8. Mechanism studies demonstrated the formation of a nickel hydride intermediate.