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

Thionyl tetrafluoride (SOF ) 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 SOF to include organolithium nucleophiles, and demonstrate, for the first time, the controlled projection of sulfur-carbon links at the sulfur center of SOF -derived iminosulfur oxydifluorides (R -N=SOF ). This method provides rapid and modular access to sulfonimidoyl fluorides (R -N=SOFR ), 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.