Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
Facultad de Química, Universidad de Oviedo, Spain.
Angew Chem Int Ed Engl. 2017 Jun 26;56(27):8004-8008. doi: 10.1002/anie.201703611. Epub 2017 Jun 1.
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 Csp3 -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.
一种前所未有的方法，利用分子碘和光氧化还原催化之间的协同相互作用，已经被开发用于双重光激活的分子内苄基 C-H 胺化反应。碘作为催化剂，通过在可见光照射下激活远程 Csp3-H 键（1,5-HAT 过程）来形成新的 C-N 键，而有机光氧化还原催化剂 TPT 则实现分子碘催化剂的再氧化。为了解释两个涉及的光化学步骤的兼容性，通过计算方法阐明了关键的 N-I 键活化。这种新的协同催化对于非金属主族催化与光催化的结合具有重要意义。
