Radical 1‐Fluorosulfonyl‐2‐alkynylation of Unactivated Alkenes

Sulfonyl fluorides have found widespread use in chemical biology and drug discovery. The development of synthetic methods for the introduction of the sulfonyl fluoride moiety is therefore of importance. Herein, a transition‐metal‐free radical 1,2‐difunctionalization of unactivated alkenes via FSO(2)‐radical addition with subsequent vicinal alkynylation to access β‐alkynyl‐fluorosulfonylalkanes is presented. Alkynyl sulfonyl fluorides are introduced as highly valuable bifunctional radical trapping reagents that also serve as FSO(2)‐radical precursors. The β‐alkynyl‐fluorosulfonylalkanes obtained in these transformations can be readily diversified by using SuFEx click chemistry to obtain sulfonates and sulfonamides.