Enantioselective Hydroalkylation of α,β-Unsaturated Amides through Reversed syn-Hydrometallation of NiH

Enantioselective synthesis of a wide range of structurally diverse β-chiral amides has been achieved through nickel-catalyzed regio-reversed hydroalkylation of α,β-unsaturated amides with alkyl iodides in the presence of a hydrosilane. Different from the classical homolysis/enantioconvergent recombination process of Ni(III) intermediates as the enantio-determining step, chiral induction in this reductive hydroalkylation was achieved through an enantiodifferentiating regio-reversed syn-hydrometallation process of α,β-unsaturated amides.