Photochemical Fluoroalkylation and Alkylthiolation of <i>O</i>‐Cyano and <i>O‐</i>Alkynyl Acrylamides: Pendant Functionality Led Divergence in Annulations

Abstract A visible‐light‐mediated, organophotocatalyzed cascade perfluoroalkylation and alkylthiolation of o ‐cyano and o ‐alkynyl acrylamides is reported. The reaction exhibits wide scope and provides polyfluorinated 1,3‐quinoline diones and trifluoromethylated fused tricyclic quinolinones under mild reaction conditions and in good yields. Access to a variety of molecular architectures and the synthetic application of aliphatic thiols are the highlights of this reactivity manifold.