Hypervalent Iodine Mediated Sulfonamide Synthesis

Abstract

A new metal‐free sulfonylation reaction is described. The method takes advantage of the Umpolung reactivity and group‐transfer properties of iodine(III) compounds, combining hypervalent iodine reagents and sulfinate salts to deliver a clean and mild transfer of sulfonyl groups to amines and anilines. A total of 25 sulfonamides was synthesised in up to 99 % yield, even on gram‐scale. The reaction mechanism was investigated by ESI‐MS and DFT calculations.

Practical synthesis and biological screening of sulfonyl hydrazides

“…Chlorobenziodoxolone ( 1 ) was prepared according to a reported procedure and used in combination with the sodium phenyl sulfinate salt ( 2a ) and 4-aminomorpholine ( 3a ) as the model substrates. The study was initiated by applying our previously described conditions for sulfonamide synthesis 14 (Table 1, entry 1). Accordingly, chlorobenziodoxolone ( 1 ) was used as the limiting reagent and mixed with the sodium phenyl sulfinate salt ( 2a ) and tetrabutylammonium iodide, in dichloromethane, under a nitrogen atmosphere, leading to N -morpholino-benzenesulfonamide ( 4aa ) and the dimorpholinodiazene ( 5a ) in 29% and 24% yields, respectively.…”

An Efficient and Practical Construction of S−N Bond from Aryl Thioureas and Amines under Metal‐Free Conditions

“…Based on the information obtained from the controlled experiments and literature reports, [14,21] we propose a possible reaction mechanism for the reaction (Scheme 3). Under the presence of K 2 CO 3 , the substrate A would be converted to B, which made the S atom more nucleophilic and therefore reacted easily with PIDA to give the active intermediate C. Subsequently, amine would attack the active intermediate C to furnish the product D and the by-products (iodobenzene and AcOH).…”

Cyclic Haloiodanes: Syntheses, Applications and Fundamental Studies

“…Marques and co‐workers have used chloroiodane 1b as a reagent for the oxidative coupling of sulfinate salts with secondary amines to form sulfonamides ( Scheme 63). [81] The method supports a broad range of amine derivatives. Benzotriazole could also be coupled with sodium phenylsulfinate in 57 % yield.…”