Cooperative Light‐Activated Iodine and Photoredox Catalysis for the Amination of C [Formula: see text] −H Bonds

An unprecedented method that makes use of the cooperative interplay between molecular iodine and photoredox catalysis has been developed for dual light‐activated intramolecular benzylic C−H amination. Iodine serves as the catalyst for the formation of a new C−N bond by activating a remote C [Formula: see text] −H bond (1,5‐HAT process) under visible‐light irradiation while the organic photoredox catalyst TPT effects the reoxidation of the molecular iodine catalyst. To explain the compatibility of the two involved photochemical steps, the key N−I bond activation was elucidated by computational methods. The new cooperative catalysis has important implications for the combination of non‐metallic main‐group catalysis with photocatalysis.