A Clickable Assembly of Enamide‐Functionalized Allylic and Vinyl Sulfonyl Fluorides With Exclusive Selectivity

A practical and efficient method was developed for the selective construction of allylic and vinyl sulfonyl fluorides. This protocol features mild reaction conditions, modular access to valuable “clickable” handles in moderate to excellent yields (60%–99%), and a broad substrate scope with functional group compatibility. Subsequently, the resulting sulfonyl fluorides were further diversified via sulfur fluoride exchange (SuFEx) reactions to produce sulfonates, sulfonamide, and enabled the late‐stage modification of bioactive molecules, showcasing their immediate value for application in chemical biology and drug discovery.