Photoinduced radical Truce-Smiles rearrangement driven by halogen bond interactions.

Herein, we report a halogen-bond-assisted catalyst-free protocol for the difluoroalkylation of alkenes via a radical Truce-Smiles rearrangement. It was found that the amine plays a dual role as a halogen-bond donor as well as a precursor of α-amino alkyl radicals, which act as reductants. Key advantages of this protocol include mild reaction conditions, broad substrate compatibility, and the potential for further applications in the synthesis of pharmaceutically relevant molecules.