Catalyst‐Free Visible Light‐Driven Hydrosulfonylation of Alkenes and Alkynes with Sulfonyl Chlorides in Water

Abstract A convenient and sustainable method for synthesizing sulfonyl‐containing compounds through a catalyst‐free aqueous‐phase hydrosulfonylation of alkenes and alkynes with sulfonyl chlorides under visible light irradiation is presented. Unactivated alkenes, electron‐deficient alkenes, alkyl and aryl alkynes can be hydrosulfonylated with various sulfonyl chlorides at room temperature with excellent yields and geometric selectivities by using tris(trimethylsilyl)silane as a hydrogen atom donor and silyl radical precursor to activate sulfonyl chlorides. Mechanistic studies revealed that the photolysis of tris(trimethylsilyl)silane in aqueous solution to produce silyl radical is crucial for the success of this reaction.