Effective Formation of New C(sp2)−S Bonds via Photoactivation of Alkylamine-based Electron Donor-Acceptor Complexes

An effective approach for the direct thiolation of five-membered heteroarenes involving visible-light-absorbing EDA complexes is reported. The reaction takes place from an EDA complex between an alkylamine and the heteroarene halide. Selective photolysis to the EDA complex has allowed to generate the heteroarene radical that is suitably trapped by disulfide derivatives, providing a potent synthetic versatility.