Radical Bicyclization of 2‐Cyanoaryl Acrylamides with Dicumyl Peroxide

A radical bicyclization of 2‐cyanoaryl acrylamides with dicumyl peroxide has been developed for constructing a broad spectrum of benzo[h]naphtho[1,8‐bc][1,6]naphthyridine. This reaction allows the formation of three new chemical bonds through addition of methyl radical across alkene double bond, intramolecular addition of carbon‐centered radical to cyano group and cyclization of the iminyl radical cascade, and features simple reaction system and wide substrate scope.