NiH-Catalyzed Proximal-Selective Hydroamination of Unactivated Alkenes

Reported herein is a modular, NiH-catalyzed
system capable of proximal-selective hydroamination of unactivated
alkenes with diverse amine sources. The key to the successful implementation
of this approach is the promotion of NiH insertion into even highly
substituted olefins via coordination of the bidentate directing group
to the nickel complex. A wide range of primary and secondary amines
can be installed in both internal and terminal unactivated alkenes
with excellent regiocontrol under the optimized reaction conditions.
This protocol is flexible and general for the preparation of a variety
of valuable β- and γ-amino acid building blocks that would
otherwise be difficult to synthesize. The utility of this transformation
was further demonstrated by the site-selective late-stage modification
of complex and medicinally relevant molecules. Combined experimental
and computational studies illuminate the detailed reaction mechanism.