Visible-Light-Triggeredand Rhodamine B‑CatalyzedThiolation of Bromoalkynes: Accessing Alkynyl Thioethers

A visible-light-mediated C(sp)–S^II <i>cross</i>-coupling of 1-haloalkynes with aryl/alkyl thiols is reported. The reaction was catalyzed by Rhodamine B under purple LED irradiation in an open-air atmosphere. Rhodamine B is a basic xanthene dye that is easily degradable and highly soluble in water. A wide range of 1-haloalkynes efficiently coupled with aryl and alkyl thiols, obtained corresponding alkynyl thioethers in moderate to excellent yields. Metal-free, room temperature, easy operation, and broad substrate scope are the salient features of the established protocol.