Visible‐Light‐Promoted Radical Tetrafluoroethylation/Cyclization of N ‐Alkenyl Indoles: Access to Tetrafluoroethylated Pyrrolo[1,2‐ a ]indoles

Tetrafluoroethylated motifs are increasingly widespread in pharmaceuticals, agrochemicals, and functional materials. However, efficient and sustainable methods for their incorporation into complex polycyclic frameworks remain underdeveloped. Herein, we report a visible‐light‐promoted radical cascade cyclization of N ‐alkenyl indoles using readily available 1,2‐dibromotetrafluoroethane (BrCF 2 CF 2 Br) as a tetrafluoroethyl radical source. This mild protocol enables a facile one‐step construction of tetrafluoroethylated pyrrolo[1,2‐ a ]indoles bearing a quaternary carbon center. The reaction exhibits broad functional group tolerance, delivering the desired products in up to 95% isolated yield. Mechanistic studies support a photoredox radical cascade pathway. This work offers a sustainable and operationally simple approach to pharmaceutically relevant fluorinated polycyclic indoles from easily accessible starting materials.