Photogeneration of thiyl radicals using metal‐halide perovskite for highly efficient synthesis of thioethers

Abstract Recently, the use of metal‐halide perovskite (MHP) for photoinduced organics transformation has attracted much attention. We report herein the development of photoinduced thiol‐ene reaction using inorganic MHP of CsPbBr 3 nanocrystal that is visible light‐responsive, easy‐to‐prepare, and cost‐effective. Under blue light‐emitting diode (LED), a series of thiol substrates are demonstrated to be highly efficient reaction partners to couple with alkenes tolerated with various functional groups, affording diverse thioethers containing C–S bonds. The CsPbBr 3 ‐mediated thiol‐ene reaction is characterized by high efficiency, broad substrate applicability, excellent yields, and mild conditions. Mechanism investigation shows that the visible light‐excited CsPbBr 3 induces the generation of thiyl radicals via hole oxidation to initiate the reaction, followed by redox neutral pathway and/or chain transfer pathway to accomplish thiol–olefin coupling. It is notable that CsPbBr 3 exhibits advanced thiol‐ene performance than that using MHP analogs and others. The work presents a new exploration of MHP‐mediated transformation and shows great potential of MHPs for radical chemistry.