An organophotoredox-catalyzed anti-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 N-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.
Pradhan et al. (Tue,) studied this question.