Research Progress on the Synthetic Applications of Direct Construction of Sulfonyl Fluoride Functional Groups Using

doi:10.6023/cjoc202409035

Abstract

Sulfonyl fluoride compounds have garnered significant attention due to their unique biological activity and reactivity. The sulfonyl fluoride functional group is typically introduced by constructing S—F bond. In recent years, the rise of the click chemistry concept has provided chemists with a novel approach, utilizing “SO₂F” reagents to directly introduce the sulfonyl fluoride functional group into molecular structures, balancing both reaction selectivity and synthetic efficiency. This review provides an overview of the synthesis and applications of various “SO₂F” reagents developed in recent years.

Key words: sulfonyl fluoride compounds, sulfuryl fluoride, fluorosulfuryl imidazolium salt, click chemistry

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Zhe Han, Yin Cui, Chengrong Ding, Jian Yang, Guofu Zhang. Research Progress on the Synthetic Applications of Direct Construction of Sulfonyl Fluoride Functional Groups Using "SO₂F" Sources[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2245-2264.

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Fig. & Tab. 64

Scheme 1. General methods for the preparation of sulfonyl fluoride compounds

Scheme 2. Production of aryl fluorosulfates from phenols trea- ted with SO2F2

Scheme 3. Synthesis of 2-(diphenyl)phosphanyl phenyl fluoro- sulfate

Scheme 4. Conversions of aryl silyl ethers to diarylsulfates

Scheme 5. SO2F2-promoted one-pot transformations of phenols into the corresponding biaryls

Scheme 6. SO2F2-promoted one-pot transformations of phenols into biarylamines

Scheme 7. Deoxy fluorination of phenols using SO2F2 and Me4NF

Scheme 8. SO2F2-mediated one-pot synthesis of aryl carboxylic acids and esters from phenols through a Pd-catalyzed insertion of carbon monoxide

Scheme 9. SO2F2-promoted Pd-catalyzed amidation of phenols

Scheme 10. Nickel-catalyzed carboxylation of aryl and heteroaryl fluorosulfates using carbon dioxide

Scheme 11. SO2F2-promoted Pd-catalyzed dehydroxylative cyanation reaction

Scheme 12. Nickel- and palladium-catalyzed cross-coupling of aryl fluorosulfonates and phosphites

Scheme 13. SO2F2-mediated oxidative dehydrogenation and dehydration of alcohols to alkynes

Scheme 14. SO2F2-promoted selective oxidation of alcohols

Scheme 15. Pd-catalyzed direct dehydroxylative cross-coupling of benzylic alcohols and aryl boronic acids

Scheme 16. SO2F2-mediated dehydrative cross-coupling of alcohols with electron-deficient olefins using a Pd-catalyst

Scheme 17. SO2F2-promoted one-pot 1,1-dihydrofluoro-alkylation

Scheme 18. Sulfuryl fluoride-promoted thiocyanation of alcohols

Scheme 19. SO2F2-promoted deoxygenhalogenation from alcohols

Scheme 20. Synthesis of symmetrically substituted sulfamides

Scheme 21. SO2F2-promoted synthesis of N,N-disubstituted sulfamoyl fluorides

Scheme 22. SO2F2-promoted dehydration of aldoximes into nitriles

Scheme 23. SO2F2-activated efficient Beckmann rearrangement of ketoximes for accessing amides

Scheme 24. A cascade process for directly converting nitriles (RCN) to cyanamides (RNHCN) via SO2F2-activated Tiemann rearrangement

Scheme 25. Deoxyfluorination of benzaldehydes using SO2F2 and Me4NF

Scheme 26. SO2F2-promoted Bamberger rearrangement of N-arylhydroxylamines

Scheme 27. SO2F2-promoted synthesis of arenesulfonyl fluorides

Scheme 28. Synthesis of sulfonyl fluorides from sulfuryl fluoride and Grignard reagents

Scheme 29. β-Sulfonamidation of ketones via SuFEx process and 1,3-rearrangement

Scheme 30. Synthesis of fluorosulfuryl imidazolium salt A

Scheme 31. Synthesis of fluorosulfonate using fluorosulfonamide imidazolium salt

Scheme 32. Synthesis of sulfamoyl fluorides from fluorosulfuryl imidazolium salt and secondary amines

Scheme 33. Synthesis of sulfamoyl fluorides from fluorosulfuryl imidazolium salt and primary amines

Scheme 34. Synthesis of novel pesticidal N,N'-disubstituted sulfamide derivatives using sulfur(VI) fluorine exchange click reaction

Scheme 35. Efficient synthesis of azidos using fluorosulfuryl azide diazotransfer reagent

Scheme 36. Efficient synthesis of azido sugars using fluorosulfuryl azide diazotransfer reagent

Scheme 37. Photoredox-catalyzed radical fluorosulfonylation of alkenes

Scheme 38. Synthesis of alkenyl or alkyl sulfonyl fluorides via fluorosulfonamidium salts

Scheme 39. Photocatalytic radical hydro-fluorosulfonylation of unactivated alkenes and alkynes

Scheme 40. Accessing FSO2-functionalized chromanes via formal endo and exo cyclization

Scheme 41. Nitrogen-oxygen bond cleavage reaction of oxime compounds promoted by “SO2F＋” donor

Scheme 42. A novel three-component reaction for constructing indolizine-containing aliphatic sulfonyl fluorides

Scheme 43. A cascade reaction for regioselective construction of pyrazole-containing aliphatic sulfonyl fluorides

Scheme 44. Enantioselective addition of azlactones to ethylene sulfonyl fluoride

Scheme 45. Regioselective conjugate addition of isoxazol-5-ones to ethenesulfonyl fluoride

Scheme 46. Ru-catalyzed C—H activation of nitrones with ethenesulfonyl fluoride

Scheme 47. Cyclobutane formation by the reaction of ethenesulfonyl fluoride with dimethyl diazomalonate

Scheme 48. Stereo- and regioselective installation of vinyl sulfonyl fluoride onto indoles without transition-metal catalyst

Scheme 49. Radical fluorosulfonylation of alkenes with FSO2Cl under photoredox conditions

Scheme 50. Visible light-induced photoredox-catalyzed chloro- fluorosulfonylation of alkynes

Scheme 51. Electrochemical-induced oxo-fluorosulfonylation of alkynes under air

Scheme 52. Electrochemical synthesis of β-keto sulfonyl fluorides via radical fluorosulfonylation of vinyl triflates

Scheme 53. Electroreductive hydroxy fluorosulfonylation of alkenes

Scheme 54. Synthesis of fluorosulfates and sulfamoyl fluorides using ASIF

Scheme 55. Synthesis and applications of vinylidene difluoro- sulfonimide (VISF)

Scheme 56. Fluorosulfuryl isocyanate enabled SuFEx ligation of alcohols and amines

Scheme 57. Diversity oriented clicking (DOC) from 2-substituted-alkynyl-1-sulfonyl fluoride (SASF) hubs

Scheme 58. DOC of SASF hubs through Michael addition pathways

Scheme 59. SASF reacting with DMSO and DMF

Scheme 60. Utilizing SASF for the difunctionalization of olefins

Scheme 61. EnT-mediated N—S bond homolysis of a bifunctional reagent leading to aliphatic sulfonyl fluorides

Scheme 62. Switchable hydro- and carbo-fluorosulfonylation

Scheme 63. Direct fluorosulfonamidation of (hetero)arenes and alkenes with photoredox-active fluorosulfamoyl radical reagents

Scheme 64. Palladium-catalyzed remote hydrosulfonamidation of alkenes

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“SO₂F”源直接构建磺酰氟官能团的合成应用研究进展