The Sulfinylsulfonation of alkynes for β‐Sulfinyl alkenylsulfone

Abstract

Here we report the sulfinylsulfonation of alkynes to afford β-sulfinyl alkenylsulfone products with a broad substrate scope, excellent functional group compatibility, and high yield. Moreover, the sulfinylsulfonation reaction of enyne can also be realized for constructing functionalized carbo-and heterocycles through a radical cascade cyclization process.

Iron-Catalyzed C(Sp3)–H Borylation, Thiolation, and Sulfinylation Enabled by Photoinduced Ligand-to-Metal Charge Transfer

“…To capture the key intermediates involved in the C­(sp 3 )–H thiolation and sulfinylation reactions, we carried out a series of control experiments, which began with activation of the sulfinate salts with acetyl chloride (Scheme c) . Interestingly, in the presence of a small amount of H 2 O, two equivalents of sulfinate salts underwent a fast reaction to give thiosulfonate ( 159 ) in 70% yield, with only trace of sulfinyl sulfone ( 160 ) observed.…”

Exploring the synthetic application of sulfinyl radicals

“…Zhang et al improved the above-mentioned sulfinyl sulfones' preparation method in 2022, making this sulfinyl radical precursor suitable for the sulfinylsulfonation of alkynes containing nucleophilic groups, such as hydroxyl and amino groups. 93 In the same year, Wu's group developed an efficient method for constructing arylalkyl sulfoxides via the cross-coupling reaction of the sulfinyl radical with the carbon-centered radical (Fig. 16B).…”

Synthesis of gem-Disulfonyl Enamines via an Iminyl-Radical-Mediated Formal 1,3-HAT/Radical Coupling Cascade

“…This pathway involves initial sulfonyl radical addition, a formal 1,3-HAT, and radical/radical coupling. The reaction of sulfinate salt with acetyl chloride is known to generate sulfonyl radical A , which was investigated in our previous work . Thus, we promptly use the sulfonyl radical A model to study the following processes in this work.…”

“…Initially, TsNa reacted with CH 3 COCl to generate sulfinyl sulfones and homolytic scission of the S–S bond in sulfinyl sulfones produced sulfonyl radical ( A ) and sulfinyl radical ( A′ ). Subsequently, the vinyl azide 1 is assaulted by A , resulting in a radicalized carbon I , which quickly transforms into iminyl radical II with N 2 release. At the same time, sulfinyl radical A′ readily undergoes homodimerization to form thiosulfonates .…”