Electrochemical Methylthiolation of Terminal Alkynes Using Dimethyl Sulfoxide

A protocol for terminal alkyne methylthiolation has been developed, utilizing an electrochemical strategy with dimethyl sulfoxide as both the solvent and the methylthiolating reagent. This organic electrochemical reaction, which employs commercially available reagents, proceeds efficiently at room temperature under transition‐metal‐free, external oxidant/reductant‐free, and base‐free conditions. The method affords a diverse array of alkyne sulfides in satisfactory yields and exhibits broad functional group compatibility.