Photoinduced α‐C−H Amination of Cyclic Amine Scaffolds Enabled by Polar‐Radical Relay

Abstract Herein, we report a polar‐radical relay strategy for α‐C−H amination of cyclic amines with N ‐chloro‐ N ‐sodio‐carbamates. The relay is initiated by in situ generation of cyclic iminium intermediate using N ‐iodosuccinimide (NIS) oxidant as an initiator, which then operates through a series of polar (addition and elimination) and radical (homolysis, hydrogen‐ and halogen atom transfer) reactions to enable the challenging C−N bond formation in a controlled manner. A broad range of α‐amino cyclic amines were readily accessed with excellent regioselectivity, and the superb applicability was further demonstrated by functionalization of biologically relevant compounds.