Organophotoredox-Catalyzed Alkylation of Vinylsulfur Pentafluoride: Expanding Access to SF ₅ -Containing Aliphatic Molecules

The pentafluorosulfanyl (SF₅) group is a valuable fluorinated motif, but aliphatic SF₅ synthesis remains challenging. We report a metal-free organophotoredox strategy to access aliphatic SF₅ compounds via alkylation of vinylsulfur pentafluoride, prepared from an SF₅-triflate precursor. This operationally simple transformation proceeds under mild conditions, tolerates a broad range of functional groups, and affords diverse SF₅-substituted alkanes in moderate to good yields. The reaction is amenable to continuous-flow processing.