A visible‐light‐induced radical tandem difluoroalkylation/cyclization to construct CF2‐containing isoquinolinonedione skeletons with methacryloyl benzamides is developed. Broad substrate scopes are compatible with metal‐, oxidant‐ and photocatalyst‐free conditions under room temperature in good‐to‐excellent yields. Mechanistic analysis revealed that the transformation is initiated by photoinduced electron donor‐acceptor (EDA) complexes formation.

Photoinduced EDA Complex‐initiated Synthesis of Fluoroalkylated Isoquinolinonediones