Photocatalytic [2+2+m] Cyclization of 2‐Cyanoaryl Acrylamides with 2‐Bromocarbonyls Involving C(sp3)–H Functionalization

Abstract An oxidant‐free photocatalytic [2+2+m] cyclization of 2‐cyanoaryl acrylamides with 2‐bromocarbonyls is reported, enabling the assembly of biologically important N‐heterocycle‐fused quinolinones including benzo[1,6]naphthyridinones and pyrrolo[3,2‐ c ]‐quinolines. This photocatalytic protocol proceeds through a radical relay pathway including alkene difunctionalization along with an intramolecular cyano insertion and subsequent site‐specific functionalization of inert C( sp 3 )−H bond enabled by cyano‐derived iminyl radical‐mediated 1,n‐hydrogen atom transfer. Notably, this transformation selectively formed two distinct C−C bonds, one C−N bond, and one quaternary carbon center in a one‐pot procedure.