LMCT–homolysis-enabled C–H functionalization of arylamines†

Herein, we report a method for metal-catalyzed para-Csp²–H functionalization of arylamines through photoinduced ligand-to-metal charge transfer (LMCT) for prospective application. The photo-LMCT–homolysis mode allows Sc–N complexes to form nitrogen radical intermediates, which are then isomerized into aryl radicals and prepared for subsequent radical coupling. A selective construction of C–O, C–S, C–Se, and C–C bonds has been achieved, and these reactions offer operationally simple, low-catalyst, and highly regioselective procedures for accessing valuable arylamine functionalization in a single step.