Photochemical Fluoroalkylation and Alkylthiolation of o‐Cyano and o‐alkynyl Acrylamides: Pendant Functionality Led Divergence in Annulations

A visible‐light‐mediated, organophotocatalyzed cascade perfluoroalkylation and alkylthiolation of o‐cyano and o‐alkynyl acryla‐mides 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.