Research Progress on the Synthesis of Sulfonyl Fluoride Compounds Based on Small Molecule Sulfur-Fluoride Building Blocks

doi:10.6023/cjoc202407019

Abstract

The sulfur-fluoride exchange click chemistry, as an emerging synthetic technique, has developed rapidly since its inception in 2014. Leveraging the sulfonyl fluoride group, this technology enables efficient and rapid synthesis of sulfonyl compounds. Sulfonyl fluorides, owing to their unique electrophilic properties, have found widespread applications in fields such as organic synthesis, chemical biology, new drug discovery, and novel material development. In recent years, sulfur-fluoride exchange click chemistry not only has facilitated the synthesis of high-value sulfur-fluoride compounds but also has been successfully applied in the research of anti-tumor, anti-bacterial, anti-oxidant, and other drugs, significantly enhancing the biological activity of these medications. Drawing upon the design and development of small-molecule sulfur-fluoride building blocks, the author provides a detailed account of the synthesis of sulfonyl fluorides in recent years. As key intermediates, sulfonyl fluorides will play a pivotal role in numerous high-tech sectors, driving the continuous advancement of chemistry, materials science, and biomedical research.

Key words: sulfur-fluoride exchange, click chemistry, sulfonyl fluoride, sulfur-fluoride building blocks

Cite this article

Jing Leng, Hao Huang, Jie Xu, Huali Qin. Research Progress on the Synthesis of Sulfonyl Fluoride Compounds Based on Small Molecule Sulfur-Fluoride Building Blocks[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1223-1238.

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Fig. & Tab. 40

Scheme 1. Synthesis of sulfonyl fluoride compounds through fluorine-chlorine exchange

Scheme 2. Chemical synthesis of ESF

Scheme 3. Michael addition reaction of nucleophiles to ESF

Scheme 4. Diels-Alder reaction of ESF with cyclic olefins and furans

Scheme 5. [2＋2] cycloaddition reaction between ESF and maleimide

Scheme 6. Radical addition reaction of ESF with carboxylic acid under photocatalysis

Scheme 7. Synthesis of 2-substituted vinyl sulfonyl fluorides via heck coupling reaction

Scheme 8. Rhodium(III)-catalyzed site-selective C—H activation for the synthesis of 2-arylvinyl sulfonyl fluorides

Scheme 9. Palladium-catalyzed non-directed C—H activation for the synthesis of 2-arylvinyl sulfonyl fluorides

Scheme 10. Synthetic route to BESF

Scheme 11. Cycloaddition, Michael addition, and Suzuki coupling reactions involving BESF

Scheme 12. Cyclization reactions of DESF with oximes, azides, and amines

Scheme 13. Cycloaddition reaction of BESF with azides

Scheme 14. Cycloaddition reactions of BESF with heterocyclic nitrogen compounds

Scheme 15. Synthesis and applications of ASF

Scheme 16. Synthesis and applications of BTESF

Scheme 17. Synthesis of SASF and its application in the field of DOC synthesis

Scheme 18. Radical addition reaction of SASF with olefins

Scheme 19. Synthesis and application of BDF

Scheme 20. Reaction of SO2F2 with phenols/phenol ethers

Scheme 21. Reaction of SO2F2 with ketones/ phenols

Scheme 22. Reaction of SO2F2 with hydroxylamine

Scheme 23. Reaction of SO2F2 with nitrogen nucleophiles

Scheme 24. Reaction of SO?F? with enyne precursor and amine

Scheme 25. Reaction between SO?F? and Grignard reagent

Scheme 26. Synthesis of FDIT and its reactive properties

Scheme 27. Synthesis and application of FSAP

Scheme 28. Synthesis and application of EDSF

Scheme 29. Synthesis and application of MeO-ESF

Scheme 30. Synthesis and application of BCASF

Scheme 31. Synthesis and application of CESF

Scheme 32. Application of BPESF in cyclization reactions

Scheme 33. Addition reaction of ClSO2F with olefins

Scheme 34. Addition reaction of ClSO2F with alkynes

Scheme 35. Synthesis and application of FSI

Scheme 36. Synthesis and application of FABI

Scheme 37. Tandem addition reaction of FABI with two molecules of olefins

Scheme 38. Synthesis and application of MDSF

Figure 39. Synthesis and application of MDF

Scheme 40. Synthesis of AISF and its reactive properties

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