Nickel-Catalyzed Regio- and Enantioselective Hydroamination of Unactivated Alkenes Using Carbonyl Directing Groups

The asymmetric addition of an N-H bond tovarious alkenes via a direct catalytic method is a powerful way ofsynthesizing value-added chiral amines. Therefore, the enantio- andregioselective hydroamination of unactivated alkenes remains anappealing goal. Here, we report the highly enantio- andregioselective Ni-catalyzed hydroamination of readily availableunactivated alkenes bearing weakly coordinating native amides oresters. This method succeeds for both terminal and internalunactivated alkenes and has a broad amine coupling partner scope.The mild reaction process is well suited for the late-stagefunctionalization of complex molecules and has the potential to gain modular access to enantioenriched beta-or gamma-amino acidderivatives and 1,2- or 1,3-diamines. Mechanistic studies reveal that a chiral bisoxazoline-bound Ni specie effectively leveragescarbonyl coordination to achieve enantio- and regioselective NiH insertion into alkenes.

Automated summary

This study reports a highly enantio- and regioselective Ni-catalyzed hydroamination of unactivated alkenes. It is applicable to common but unreactive alkenes and has a broad range of amine coupling partners, showing great potential for late-stage functionalization of complex molecules.