Electroreductive Hydroselenization/Hydrosulfuration of Vinyl Sulfones for the Synthesis of β‐Selenosulfones and β‐Thiosulfones

An environmentally benign electrochemical reductive method has been developed for the hydroselenization/hydrosulfuration of vinyl sulfones with diselenides/disulfides. The reaction proceeds smoothly in an undivided cell at room temperature in open air, without the need for metal catalysts or oxidants, achieving yields of up to 99% for 37 β‐selenosulfones and β‐thiosulfones. This strategy is also applicable to other electron‐deficient olefins, providing a mild and efficient approach for constructing C─Se and C─S bonds.