Nickel-Catalyzed Enantioselective Reductive Amination of Ketones with Both Arylamines and Benzhydrazide

An asymmetric reductive amination of ketones using both arylamines and benzhydrazide in the presence of nickel catalysts was developed. A one‐pot synthesis of tetrahydroquinoxalines was also developed starting directly from α‐ketoaldehydes and 1,2‐diaminobenzene. Formic acid was used as a safe and economic surrogate for high‐pressure hydrogen gas. Strongly σ‐donating bis(alkylphosphine)s are crucial ancillary ligands for both stereoselective hydride insertion and decarboxylation of the formate. Reducing costs: Reductive amination of ketones with both arylamines and benzhydrazide was realized in the presence of catalysts based on nickel rather than expensive noble metals. Formic acid was used as a safe and cheap surrogate for high‐pressure hydrogen gas.