Iron-Catalyzed\nMarkovnikov-Selective Radical Hydrochalcogenation\nof Unactivated Alkenes

A Markovnikov-selective radical hydrochalcogenation reaction\nof\nunactivated alkenes via iron-catalyzed hydrogen atom transfer was\nreported. Using <i>N</i>-(arylsulfenyl)arenesulfonamide,\nPhSO<sub>2</sub>SCD<sub>3</sub>, <i>S</i>-alkyl thiosulfonate, <i>S</i>-alkyl dithiosulfonate and Ebselen derivatives as versatile\nradicalophiles, a wide range of unsymmetrical alkyl-aryl, dialkyl\nand SCD<sub>3</sub> (D > 99%) containing sulfides, dialkyl disulfides,\nas well as organoselenides have been collectively synthesized under\nmild conditions. As a powerful alternative to the classical thiol–ene\nreaction, this protocol features exclusive Markovnikov selectivity,\ngood functional group tolerance and broad substrate scope. A number\nof radical probe experiments suggest the hydrochalcogenation proceeds\nthrough the radical pathway. The synthetic utility of this transformation\nwas also demonstrated through the late-stage modifications of diverse\nnatural products and bioactive molecules.