Remote and Proximal Hydroaminoalkylation of Alkenes Enabled by Photoredox/Nickel Dual Catalysis.

A mild and site-selective hydroaminoalkylation of activated and unactivated alkenes via dual photoredox/Ni catalysis is developed. This dual catalytic strategy enables exclusive access to α-selective products, which is complementary to previously reported photocatalytic hydroaminoalkylation of activated alkenes that provides the β-selective products. The chain-walking of a Ni-H intermediate toward a carbonyl allows for the hydroaminoalkylation of unactivated alkenes at remote sp 3 C-H sites. This method tolerates a broad substrate scope of both amines and alkenes as well as providing a streamlined synthesis of value-added β-amino acid derivatives from readily available starting materials.