Visible Light‐Induced Oxygen‐Doped g‐C₃N₄ Catalyzed Aryltrifluoromethylation of Unactivated Alkenes with CF₃SO₂Na: A Heterogeneous and Recyclable Approach Without Metals or Oxidants

Utilizing metal‐free heterogeneous photocatalysts to convert solar energy into chemical energy and achieve efficient organic transformations through redox processes remains a long‐standing challenge. With visible light‐responsive oxygen‐doped g‐C 3 N 4 as a heterogeneous photocatalyst, a metal‐ and oxidant‐free trifluoromethylation/cyclization methodology has been developed to synthesize a series of new trifluoromethylated dihydroisoquinolinones and indolines. In this system, the aryltrifluoromethylation of N‐allylbenzamides or N‐aryl‐N‐allylamides with CF 3 SO 2 Na proceeds smoothly in one pot under blue light irradiation at room temperature, affording the desired products in moderate to good yields. This semiconductor‐based photoredox system allows for trifluoromethylation/cyclization free of any metals, strong oxidants, and additives. It is applicable to gram‐scale experiments and recyclability tests without significant loss of reactivity. This methodology demonstrates great potential for constructing CF 3 ‐containing heterocycles in a green and sustainable manner.