Base‐Promoted Selective Synthesis of Alkynyl Sulfides via C−S Bond Cleavage of Alkynyl Sulfonium Salts

Abstract An effective one‐pot approach has been devised for the selective synthesis of alkynyl sulfides through the cleavage of C−S bonds in alkynyl sulfonium salts. This method involves a base‐promoted nucleophilic ring‐opening and desulfurization pathway, enabling the efficient preparation of diverse alkynyl sulfide compounds. The reaction demonstrates excellent tolerance to various functional groups and proves applicable to the late‐stage functionalization of bioactive molecules and pharmaceuticals. Moreover, the practicality of this method has been underscored through scale‐up reaction and modification of alkynyl sulfide products.