Research Progress in Free Radical Fluorosulfonylation

doi:10.6023/cjoc202407012

Abstract

As a distinctive functional group with remarkable reactivity in organic synthesis, sulfonyl fluoride has demon- strated vast application potential in numerous fields, including drug synthesis, chemical biology and materials science. Nonetheless, owing to the growing demand for environmental sustainability in modern chemical synthesis, traditional methods of sulfonyl fluoride synthesis are under reconsideration. Conversely, free radical fluorosulfonylation has emerged as a vital method of introducing the sulfonyl fluoride group, attributed to its superior efficiency, minimal energy consumption, and eco-friendliness. This article will concentrate on the recent advancements in the reaction of free radical fluorosulfonylation.

Key words: sulfonyl fluorination, free radical, visible light catalysis, electrocatalysis, click chemistry

Cite this article

Jia Zhao, Qiuyun Gan, Yaofeng Yuan. Research Progress in Free Radical Fluorosulfonylation[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1206-1222.

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Fig. & Tab. 28

Figure 1. Biologically active molecules containing sulfonyl fluoride groups

Figure 2. Reported radical sulfonyl fluoride reagents

Scheme 1. Peroxide initiated the radical fluorosulfonylation of olefins with FSO2Cl

Scheme 2. Visible light catalyzed free radical fluorosulfonylation of olefins with FSO2Cl

Scheme 3. Electrocatalyzed free radical fluorosulfonylation of alkynes with FSO2Cl

Scheme 4. Visible light catalyzed free radical fluorosulfonylvinylation of unactivated C(sp3)—H via EDA complexes

Scheme 5. Visible light catalyzed aza-Michael addition of FSO2-functionalized tetrahydropyridines

Scheme 6. Visible light catalyzed radical ring-opening fluorosulfonylation of methylenecyclobutanols

Scheme 7. Visible light catalyzed free radical hydro-fluorosulfonylation of propargylic alcohols via EDA complexes

Scheme 8. Visible light catalyzed free radical fluorosulfonyl arylation of alkynes via EDA complexes

Scheme 9. Synthesis of β-keto sulfonyl fluorides with electrocatalytic oxo-fluorosulfonylation of alkynes

Scheme 10. Mechanism of electrochemical catalytic free radical fluorosulfonylation

Scheme 11. Electrocatalytic free radical fluorosulfonylation of enol trifluoromethyl sulfonate

Scheme 12. Synthesis of β-hydroxysulfonyl fluoride with electrocatalytic radical fluorosulfonylation

Figure 3. Structures of FABI and IMSF

Scheme 13. Visible light catalyzed radical fluorosulfonylation of olefins

Scheme 14. Visible light catalyzed stereoselectivity radical fluorosulfonylation of olefins

Scheme 15. Visible light catalyzed free radical fluorosulfonylation of ene acetylene

Scheme 16. Visible light catalyzed radical fluorosulfonylation tandem cyclization of olefins

Scheme 17. Visible light-mediated free radical sulfonyl fluoro-isoarylation of alkenes

Scheme 18. Three-component radical-polarized cross-radical sulfonyl fluoride reaction of alkenes

Scheme 19. Photoredox-catalyzed stereo and regioselective vicinal fluorosulfonyl-borylation of unsaturated hydrocarbons

Scheme 20. FSO2 radical-initiated photoredox cyclization of 4-enoic acids

Scheme 21. Trifluoromethyl radical-mediated trifluoromethylated sulfonyl fluorination of alkynes

Scheme 22. AIBN catalyzed the free radical fluorosulfonylation/alkynylation of olefins

Scheme 23. Energy transfer mediated radical fluorosulfonylation of olefins

Scheme 24. Visible light catalyzed enol fluorosulfonate synthesis of β-sulfonyl fluorone

Scheme 25. Visible light catalyzed free radical sulfonyl fluoro carbonylation of olefins

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