Abstract Functionalization of N, N′-disubstituted alanylglycine anhydrides under radical conditions is described. The radical (7), generated (i) from reactions of N, N'-disubstituted alanylglycine anhydrides with N-bromosuccinimide, and (ii) from related bromo compounds by reaction with tributyltin deuteride, undergoes carbon-bromine and carbon-deuterium bond formation with moderate to high diastereoselectivities depending on the N- ...