Controllable Construction of Vinyl Sulfones and β‐Keto Selenosulfones via Selective Oxidative Sulfonylation of Alkenes

Comprehensive Summary The selective oxidative sulfonylation of alkenes with selenium sulfonate depended on the reaction conditions. The electrochemical C—H sulfonylation proceeded smoothly to afford ( E )‐vinyl sulfones with good selectivity in an undivided cell without external oxidant. While aerobic trifunctionalization of alkenes occurred in the presence of KI in the air, which provides β ‐keto selenosulfones via the formation of C—O, C—S, and C—Se bonds in one‐pot. Following control experiments, a plausible mechanism is proposed to rationalize the experimental results.