SuFEx Chemistry of Thionyl Tetrafluoride (SOF4) with Organolithium Nucleophiles: Synthesis of Sulfonimidoyl Fluorides,Sulfoximines, Sulfonimidamides,and Sulfonimidates

Thionyl tetrafluoride (SOF₄) is a valuable connective gas for sulfur fluoride exchange (SuFEx) click chemistry that enables multidimensional linkages to be created via sulfur–oxygen and sulfur–nitrogen bonds. Herein, we expand the available SuFEx chemistry of SOF₄ to include organolithium nucleophiles, and demonstrate, for the first time, the controlled projection of sulfur–carbon links at the sulfur center of SOF₄‐derived iminosulfur oxydifluorides (R¹−N=SOF₂). This method provides rapid and modular access to sulfonimidoyl fluorides (R¹−N=SOFR²), another array of versatile SuFEx connectors with readily tunable reactivity of the S−F handle. Divergent connections derived from these valuable sulfonimidoyl fluoride units are also demonstrated, including the synthesis of sulfoximines, sulfonimidamides, and sulfonimidates.