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

• Published in: Asian journal of organic chemistry Vol. 11; no. 12
• Main Authors: Yadav, Navin, Payra, Soumen, Narasimha Moorthy, Jarugu
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01-12-2022
• Subjects: Alcohols; Aromatic compounds; Chemical synthesis; Cross coupling; Esters; Hydrazides; Iodine; Organic chemistry; Oxidation; Oxone; Phenols; Sufonyl Hydrazides; Thiols; Thiosulfonates
• ISSN: 2193-5807; 2193-5815
• DOI: 10.1002/ajoc.202200554

A metal‐free and green iodine‐catalyzed protocol is described herein for the synthesis of unsymmetrical thiosulfonates by sulfonylation of thiols using I2/Oxone. It's shown that oxidative cross‐coupling of thiyl radicals with sulfonyl radicals – generated from thiols and sulfonyl hydrazides, respectively, by the redox chemistry between thiol/Oxone and I2/Oxone – occurs in a facile manner at rt, providing access to unsymmetrical thiosulfonates. Diverse unsymmetrical thiosulfonates are synthesized in good‐to‐excellent isolated yields by the reactions of aryl/(hetero)aryl/alkyl thiols with a variety of aryl/(hetero)aryl/alkyl/benzyl sulfonyl hydrazides. The protocol can be further extended to the synthesis of alkyl/aryl sulfonate esters by the reactions of sulfonyl hydrazides with alcohols/phenols using I2/Oxone.
A highly efficient iodine‐catalyzed Oxone‐mediated synthesis of unsymmetrical thiosulfonates/sulfonate esters by oxidative cross‐coupling of thiols/alcohols with sulfonyl hydrazides has been developed. This protocol is scalable, and permits good functional group tolerance and diverse substrate scope.