Dinickel-catalyzed enantioselective reductive addition of imines with vinyl halides.

Abstract

A dinickel complex-enabled, enantioselective reductive alkenylation reaction of N-Ts imines with vinyl chlorides is reported. This method is effective with a wide array of (hetero)aryl and aliphatic imines bearing diverse functional groups. Under mildly reductive conditions, synthetically valuable allylic amines are obtained in good yields with excellent enantioselectivities. Furthermore, this catalytic system can be extended to aldehydes, offering an efficient route to access chiral allylic alcohols from readily available starting materials. The potential applications of this method are demonstrated by its use in the late-stage functionalization of biologically active molecular derivatives and the manipulation of reaction products. Initial mechanistic investigations and DFT calculation lend support to a catalytic addition pathway.