ABSTRACT Sulfonyl fluorides (R─SO 2 F), as key connecting units in the S(VI)‐F exchange reaction (SuFEx), have shown great potential for applications in the fields of synthetic chemistry, drug discovery and development, materials science, and chemical biology, etc. In this paper, we systematically review the progress of synthetic methodology of sulfonyl fluoride compounds, and summarize them into three major strategies: 1. Sulfur Center Transformation Synthesis: starting from the precursors containing C─S bonds, and then constructing the ─SO 2 F functional group by means of oxidation and halogen exchange; 2. C‐S Bond Constructive Synthesis: introducing ─SO 2 F while building C─S bonds through SO 2 insertion, radical pathway, or coupling reactions; 3. Module Transfer Type Synthesis (SO 2 F‐Transfer / SuFEx): utilizing reagents that already contain ─SO 2 F for modular assembly to achieve efficient and specialized linkages. The article further discusses the applications of sulfonyl fluoride in the fields of covalent drug design, functional polymer materials, analytical chemistry and electrochemistry, etc. Finally, the future development of sulfonyl fluoride chemistry is expected, including the development of new ‐SO 2 F sources, the expansion of green synthesis pathways, and the deepening of the application in the late‐stage modification of complex molecules and the construction of smart materials.
Zhao et al. (2026) studied this question.