Photoinduced Electron Donor–Acceptor Complex Strategy for Forging CS Bond via β ‐Fragmentation of Alkoxy Radicals

A mild and highly efficient photoinduced radical−radical coupling between N ‐alkoxyphthalimides (NAPI) and aryl thiolates is reported, which proceeds without the requirement of a photocatalyst and offers distinct advantages over traditional CS bond‐forming strategies. Mechanistic studies strongly support the formation of an electron donor–acceptor (EDA) complex based on thiolates. This method provides an alternative route for the preparation of aryl–alkyl thioethers and enriches the synthetic applications of N ‐alkoxyphthalimides as alkoxy radical precursors in the construction of a wide array of CX bonds.