Iron-Catalyzed Alkylative Aminosulfonylation of Alkenes and Alkynes via Radical-Anion Relay

A novel Fe-catalyzed alkylative aminosulfonylation of alkenes and alkynes with alkyl halides and O-Ts activated hydroxylamines by using Na₂S₂O₄ as a reductant and sulfone source has been developed. The metal-electron-shuttle catalysis was discovered to be vital for the highly efficient generation of sulfonyl radicals and anions without requiring organometallic intermediates. This method provides efficient access to sulfonamides from easily available alkenes and Na₂S₂O₄ and features a broad substrate scope.