A Visible-Light Organophotoredox-Catalyzed <i>anti</i>-Markovnikov Hydrocarbamoylation of Unactivated Alkene and Cyclization Cascade via Radical Relay

An organophotoredox-catalyzed <i>anti</i>-Markovnikov addition of the carbamoyl radical generated through the homolytic cleavage of 4-carbamoyl-1,4-dihydropyridine to the challenging unactivated alkene has been developed. Interestingly, the amino acid-derived carbamoyl precursor provided a unique opportunity for <i>N</i>-terminus modification of amino acids and peptides. This mild and simple method is suitable for the seamless synthesis and late-stage modification of complex drug molecules and cascade cyclization via radical relay.