Nickel‐Catalyzed Intermolecular Carbosulfonylation of Alkynes via Sulfonyl Radicals

β,β‐Disubstituted vinyl sulfones were obtained with complete regio‐ and stereocontrol in a multicomponent reaction involving alkynes, organoboronic acids, and sulfonyl chlorides in the presence of a nickel catalyst. The reaction proceeds via sulfonyl radicals generated in situ under mild reaction conditions. Running mild: Readily available alkynes, boronic acids, and sulfonyl chlorides can be combined in the presence of a Ni catalyst to produce β,β‐disubstituted vinyl sulfones with complete regio‐ and stereocontrol. The reaction proceeds via sulfonyl radicals generated in situ under mild reaction conditions and with high functional‐group tolerance.