Asymmetric Stepwise Reductive Amination of Sulfonamides, Sulfamates, and a Phosphinamide by Nickel Catalysis

Asymmetric reductive amination of poorly nucleophilic sulfonamides was realized in the presence of nickel catalysts and titanium alkoxide. A wide range of ketones, including enolizable ketones and some biaryl ones, were converted into sulfonamides in excellent enantiomeric excess. The cyclization of sulfamates and intermolecular reductive amination of a diarylphosphinamide were also successful. Formic acid was used as a safe and economic surrogate of high-pressure hydrogen gas. Agency for Science, Technology and Research (A*STAR) Economic Development Board (EDB) We thank Singapore GSK-EDB Trust Fund (2017 GSK-EDBgreen and sustainable manufacturing award) and SingaporeA*STAR Science &Engineering Research Council (AMEIRG A1783c0010) for financial support. We thank BenAshley for some initial experiments.X.Z. and H.X. contrib-uted equally to the experiments.