Abstract Lithium 1-alkynethiolates, generated by a base-induced ring cleavage of 4- substituted 1, 2, 3-thiadiazoles, were efficiently converted into the corresponding sulfenate salts by mild oxidation using an N-sulfonyloxaziridine derived from pinacolone. In situ S- alkylation with alkyl halides led to α, β-acetylenic sulfoxides.
