Kang Hyotaik, Tan Lida, Han Jing-Tan, Huang Chia-Yu, Su Hui, Kavun Aleksei, Li Chao-Jun
Department of Chemistry, FRQNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street W., Montréal, Québec, H3A0B8, Canada.
Commun Chem. 2023 Sep 1;6(1):181. doi: 10.1038/s42004-023-00947-w.
Alkanes are naturally abundant chemical building blocks that contain plentiful C(sp)-H bonds. While inert, the activation of C(sp)-H via hydrogen atom abstraction (HAT) stages an appealing approach to generate alkyl radicals. However, prevailing shortcomings include the excessive use of oxidants and alkanes that impede scope. We herein show the use of gallium nitride (GaN) as a non-toxic, recyclable, heterogeneous photocatalyst to enable alkyl C(sp)-H in conjunction with the catalytic use of simple photosensitizer, benzophenone, to promote the desired alkyl radical generation. The dual photocatalytic cycle enables cross-dehydrogenative Minisci alkylation under mild and chemical oxidant-free conditions.
烷烃是天然丰富的化学结构单元，含有大量的C(sp)-H键。虽然呈惰性，但通过氢原子转移（HAT）活化C(sp)-H为生成烷基自由基提供了一种有吸引力的方法。然而，主要缺点包括过度使用阻碍反应范围的氧化剂和烷烃。我们在此展示了使用氮化镓（GaN）作为无毒、可回收的多相光催化剂，结合简单光敏剂二苯甲酮的催化作用，实现烷基C(sp)-H的活化，以促进所需烷基自由基的生成。这种双光催化循环能够在温和且无化学氧化剂的条件下实现交叉脱氢的米氏烷基化反应。
