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.
Keywords: SuFEx chemistry; click chemistry; organolithium reagents; sulfonimidoyl fluorides; thionyl tetrafluoride.
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