Ultrasound-Accelerated Synthesis of Asymmetrical Thiosulfonate S-Esters by Base-Promoted Reaction of Sulfonyl Chlorides with Thiols

Synthesis of Symmetrical and Unsymmetrical Thiosulfonates from Disulfides through Electrochemically Induced Disulfide Bond Metathesis and Site‐Selective Oxidation

“…The generation of unsymmetrical thiosulfonates is more challenging and can be accomplished for example by cross‐coupling of sodium sulfinates with thiols, [35,36] disulfides [37–40] or N ‐arylthiosuccinimides [41,42] . Alternatively, they can be synthesized by reaction of thiols with sulfonyl hydrazines [43–45] or by the addition of thiols to sulfonyl halides through a nucleophilic substitution [46–48] . All of these methods require the stoichiometric use of oxidants (e. g. H 2 O 2 , NaIO 4 , PIFA, I 2 , oxone, CAN), reductants (e. g. Zn, Sm, LiAlH 4 ) or the application of transition metals (e. g. Zn(II), Ag(I), Cu(I), TiCl 4 ), which is highly problematic and disadvantageous from both an ecological and an economical point of view.…”

Thiosulfonates as Emerging Reactants: Synthesis and Applications

“…Due to the toxicity of pyridine,s everal groups also screened for other bases like triethylamine (Scheme 22, route 2) in this reaction. [75] Although the use of alternative bases results in al ess toxic procedure,d isulfide (3)f ormationu nfortunately could not be prevented. Moreover, the use of diethyle ther as the solvent does not maket his af avoureds trategy for thiosulfonate (7)s ynthesis.…”

“…Due to the toxicity of pyridine, several groups also screened for other bases like triethylamine (Scheme , route 2) in this reaction . Although the use of alternative bases results in a less toxic procedure, disulfide ( 3 ) formation unfortunately could not be prevented.…”

An Expedient Iodine‐Catalyzed Synthesis of Unsymmetrical Thiosulfonates by Sulfonylation of Thiols using Sulfonyl hydrazides in the Presence of Oxone

“…[7] Of course, the reaction of sulfonyl chlorides with thiols leads to unsymmetrical thiosulfonates, albeit in low yields with persistent formation of disulfide. [8] Transition metal-based and electrochemically-promoted coupling reactions between sulfinates and thiols have also been reported for the synthesis of unsymmetrical thiosulfonates. [9a-b,d] Recently reported methods include the coupling of aryldiazonium salts with thiols in the presence of DABCO • (SO 2 ) 2 (DABSO) or sodium metabisulphite respectively, [9c,e] and use of N-hydroxyaryl sulfonamide as a sulfonylating agent of thiols in the presence of iodine.…”

“…The synthesis of unsymmetrical thiosulfonates has been accomplished by sulfur‐sulfone bond formation through the reaction between disulfides and sodium sulfinate in the presence of metal‐based oxidants such as CuI, AgNO 3 , etc., and halogen‐based oxidants such as I 2 , Br 2 , NBS, etc [7] . Of course, the reaction of sulfonyl chlorides with thiols leads to unsymmetrical thiosulfonates, albeit in low yields with persistent formation of disulfide [8] . Transition metal‐based and electrochemically‐promoted coupling reactions between sulfinates and thiols have also been reported for the synthesis of unsymmetrical thiosulfonates [9a–b,d] .…”