Abstract H 2 O 2/POCl 3 is found to be a reactive reagent system that can be used in sodium dodecyl sulfate (SDS) micellar solution in aqueous media for the direct oxidative chlorination of thiol and disulfide derivatives to give the desired sulfonyl chlorides. The oxidation of thiols and disulfides to sulfonic acids with this system is also reported. In most cases, these reactions are highly selective, simple, and clean, affording products in excellent yields and ...