SuFEx Chemistry of Thionyl Tetrafluoride (SOF 4 ) with Organolithium Nucleophiles: Synthesis of Sulfonimidoyl Fluorides, Sulfoximines, Sulfonimidamides, and Sulfonimidates

Angew Chem Int Ed Engl. 2018 Feb 12;57(7):1939-1943. doi: 10.1002/anie.201712145. Epub 2018 Jan 16.


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.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Fluorides / chemistry*
  • Imides / chemical synthesis
  • Imides / chemistry*
  • Lactones / chemical synthesis
  • Lactones / chemistry*
  • Organometallic Compounds / chemistry*
  • Sulfones / chemistry*


  • Imides
  • Lactones
  • Organometallic Compounds
  • Sulfones
  • phenyllithium
  • Fluorides