Cooperative Light-Activated Iodine and Photoredox Catalysis for the Amination of Csp3-H Bonds

An unprecedented method that makes use of the cooperative interplay between molecular iodine and photo-redox 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-sp3-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.