Photoinduced 1,2-Chlorothiolation of Unactivated Alkenes via Proton Transfer and Electron Transfer

Chlorosulfur compounds, serving as structural cores in numerous bioactive molecules, represent valuable yet synthetically challenging building blocks. Herein, we report a photoinduced 1,2-chlorothiolation of unactivated alkenes enabled by proton transfer and electron transfer processes between hydrochloric acid (HCl) and dimethylsulfoxide (DMSO). This transformation employs inexpensive, readily available, and stable thiophenols as the sulfur source and proceeds without external photocatalysts and metals, constructing chlorosulfur compounds under mild conditions with broad substrate scope, high stereoselectivity, and gram-scale capability.