A Dual Photoredox/Cobalt Catalytic System Enables Markovnikov-Selective Hydroaminoalkylation of Alkenes.

We report a visible light-driven dual photoredox/cobalt catalytic system that enables Markovnikov-selective hydroaminoalkylation of alkenes. This cooperative catalysis generates and couples two radical species derived from alkylamines and alkenes via sequential single-electron and proton transfers (SET/PT) from the α-amino C-(sp3)-H bonds of amines to alkenes. The method enables the installation of secondary or tertiary alkyl groups at α-amino positions of α-amino acid derivatives, peptides, and benzylaniline derivatives using a broad range of alkene partners. This strategy represents a conceptually distinct, redox-neutral, and atom-economical approach to hydrocarbofunctionalization beyond conventional C-H activation pathways.