Formate‐Mediated Synthesis of β‐Hydroxysulfides from Olefins and Thiosulfonates via EDA Complex Strategy under Visible Light Irradiation in Air

Comprehensive Summary A visible‐light‐induced and efficient one‐pot synthesis of β ‐hydroxysulfides from olefins, thiosulfonates and HCOOCs using an EDA complex strategy under air atmosphere at room temperature has been disclosed. A plausible radical involved mechanism is proposed. During the reaction process, formates play a crucial role: first, as donors in the EDA complex; second, as providers of the hydrogen source; and third, by generating CO 2 •– to reduce peroxide intermediates, leading to the formation of β ‐hydroxysulfides. In contrast to the previously reported thiol‐oxygen co‐oxidation reactions, this simple and sustainable approach features mild reaction conditions, operational simplicity, odorless and excellent functional group tolerance.