Visible-light-induced radical C(sp3)–S coupling for the synthesis of cyanoalkyl thioethers†

Herein, visible-light-driven radical–radical cross-coupling for the construction of a C(sp³)–S bond to afford various cyanoalkyl thioethers through EDA complex-promoted C–C and C–H bond cleavage is described. The photoactivation of a transiently assembled chromophore between thiolate anions and cycloketone oxime esters is critical to the generation of the C(sp³)–S bond. Notably, we also realize the in situ formed EDA complex-mediated 1,3-hydrogen atom transfer (HAT) to construct diverse thioethers under the standard conditions. This synthetic method features easily available substrates, a wide substrate scope, and mild reaction conditions, and has potential to be used for the preparation of valuable sulfides.