Vinyl and Bromo‐Vinyl Sulfoximine Synthesis via Reactive Sulfonimidoyl Bromide Intermediates

Vinyl sulfoximines are valuable scaffolds in drug discovery and chemical biology, but their widespread use is limited by a lack of synthetic methods. Here, a catalyst‐free, one‐pot protocol is presented for the direct synthesis of vinyl sulfoximines from readily available alkenes, thiols, and nitrogen‐containing substrates such as sulfonamides or amides under oxidative conditions using 1,3‐dibromo‐5,5‐dimethylhydantoin. This transformation proceeds via the in situ generation of reactive sulfonimidoyl bromide intermediates, which are previously unused versatile synthons that eliminate the need for pre‐functionalized halogenated precursors. Mechanistic investigations and density functional theory calculations provide support for a single‐electron transfer process between sulfonimidoyl bromide and phenylthiolate. Furthermore, using alkynes instead of alkenes allows the first synthesis of bromo‐vinyl sulfoximines, which are reactive and structurally tunable and have a synthetically versatile C–Br handle, making them promising candidates for drug discovery applications.