Metal-free transformation of phenols into substituted benzamides: A highly selective radical 1,2-O→C transposition in O-aryl-N-phenylthiocarbamates

摘要

Radical merry-go-round: A highly efficient metal-free transformation of phenols into benzamides is designed through one-step conversion of phenols to aryl thiocarbamates and a subsequent radical addition/rearrangement/ fragmentation cascade. Computational analysis fully rationalizes the experimentally observed selectivity. Despite the possible competition from N-C fragmentation and N-neophyl rearrangement, the transformation exclusively follows the most kinetically and thermodynamically favored O-neophyl rearrangement path.