Abstract

AbstractAn 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(sp3)−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.

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