Photoinduced Transformations Toward Oxindole and Isoquinolinedione Scaffolds via Orthogonal Halogen Bonding Interactions and Halogen Atom Transfer (XAT)

Herein, we report a strategy for the photoinduced halogen‐bond‐mediated activation of inert alkyl halides, enabling their participation in radical addition and cascade cyclization reactions with N ‐arylacrylamides and N ‐acryloyl benzamides. This approach affords a range of functionalized oxindoles and isoquinolinediones, including pharmaceutically relevant compounds, in good to excellent yields. Combined experimental and computational investigations reveal that halogen‐bonding interactions between amine/iodoarene and amine/alkyl halide pairs play a crucial role in facilitating the transformation. Upon light irradiation, the predominant pathway involves the generation of aryl radicals and α‐amino alkyl radicals, which subsequently activate the alkyl iodide through a halogen atom transfer (XAT) mechanism.