<i>N</i> ‐(Heptafluoroisopropylthio)saccharin as a Practical Reagent for Electrophilic –SCF(CF ₃ ) ₂ Installation

We report the multigram‐scale synthesis of a shelf‐stable, saccharin‐based reagent for the direct electrophilic installation of the heptafluoroisopropylthio (–SCF(CF 3 ) 2 ) group. This bulky, highly fluorinated motif is increasingly valued for tuning lipophilicity, polarity, and metabolic stability in agrochemical design, yet methods for its direct incorporation remain scarce. The reagent enables mild, one‐step formation of CSR F and NSR F bonds with a broad range of nucleophilic substrates, including indoles, pyrroles, phenols, and amines, exhibiting genuine electrophilic reactivity and broad functional‐group tolerance. Furthermore, oxidation of the resulting NSR F bond provides access to sulfonamide derivatives without the need for conventional sulfonyl chloride precursors. This strategy offers a practical and modular route to complex fluorinated sulfur compounds and expands the synthetic toolbox for late‐stage functionalization with valuable polyfluoroalkylthio motifs (–SR F ).