自由基磺酰氟化反应研究进展

doi:10.6023/cjoc202407012

摘要/Abstract

磺酰氟作为有机合成中具有独特反应活性的官能团, 已经在药物合成、化学生物学和材料科学等多个领域展现出巨大的应用潜力. 然而, 随着现代合成化学对于环境友好性和可持续性要求的不断提高, 传统的磺酰氟合成方法面临着越来越大的挑战. 与传统方法相比, 自由基磺酰氟化反应因其反应高效、能耗低和环境友好的特点, 逐渐成为引入磺酰氟基团的重要手段, 在有机合成中发挥出越来越重要的作用. 此综述将重点介绍自由基磺酰氟化反应方面的最新进展.

关键词: 磺酰氟, 自由基, 可见光催化, 电催化, 点击化学

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

引用此文

赵佳, 甘秋云, 袁耀锋. 自由基磺酰氟化反应研究进展[J]. 有机化学, 2025, 45(4): 1206-1222.

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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图/表 28

图1. 含磺酰氟基团的生物活性分子

Figure 1. Biologically active molecules containing sulfonyl fluoride groups

图2. 自由基磺酰氟化试剂

Figure 2. Reported radical sulfonyl fluoride reagents

图式1. 过氧化物引发FSO2Cl对烯烃的自由基磺酰氟化反应

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

图式2. 可见光催化FSO2Cl对烯烃的自由基磺酰氟化反应

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

图式3. 电催化FSO2Cl对炔烃的自由基磺酰氟化反应

Scheme 3. Electrocatalyzed free radical fluorosulfonylation of alkynes with FSO2Cl

图式4. 可见光催化EDA络合物对未活化C(sp3)—H的自由基氟磺酰乙烯基化反应

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

图式5. 可见光催化磺酰氟功能化四氢吡啶的氮杂迈克尔加成反应

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

图式6. 可见光催化亚甲基环丁醇的自由基开环磺酰氟化反应

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

图式7. 可见光催化EDA络合物对炔丙醇的自由基氢磺酰氟化反应

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

图式8. 可见光催化EDA络合物对炔烃的自由基氟磺酰芳基化反应

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

图式9. 电化学催化炔烃的自由基氧磺酰氟化反应合成β-氟磺酰基酮

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

图式10. 电化学催化自由基磺酰氟化反应机理

Scheme 10. Mechanism of electrochemical catalytic free radical fluorosulfonylation

图式11. 电化学催化烯醇三氟甲基磺酸酯的自由基磺酰氟化反应

Scheme 11. Electrocatalytic free radical fluorosulfonylation of enol trifluoromethyl sulfonate

图式12. 电化学催化自由基磺酰氟化反应合成β-羟基磺酰氟

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

图3. 苯并咪唑鎓氟磺酸阳离子盐的结构式

Figure 3. Structures of FABI and IMSF

图式13. 可见光催化烯烃的自由基磺酰氟化反应

Scheme 13. Visible light catalyzed radical fluorosulfonylation of olefins

图式14. 可见光催化烯烃的立体选择性自由基磺酰氟化反应

Scheme 14. Visible light catalyzed stereoselectivity radical fluorosulfonylation of olefins

图式15. 可见光催化烯炔的自由基磺酰氟化反应

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

图式16. 可见光催化烯烃的自由基磺酰氟化串联环化反应

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

图式17. 可见光介导的烯烃的自由基磺酰氟异芳基化反应

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

图式18. 烯烃的三组分自由基-极化交叉自由基磺酰氟反应

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

图式19. 光氧化还原催化不饱和烃的立体和区域选择性邻位磺酰氟硼化反应

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

图式20. 可见光催化FSO2自由基引发4-烯酸的环化反应

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

图式21. 三氟甲基自由基介导的炔烃的三氟甲基化磺酰氟化反应

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

图式22. AIBN催化烯烃的自由基磺酰氟化/炔基化反应

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

图式23. 能量转移介导的烯烃的自由基磺酰氟化反应

Scheme 23. Energy transfer mediated radical fluorosulfonylation of olefins

图式24. 可见光催化合成β-磺酰氟酮

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

图式25. 可见光催化烯烃的自由基磺酰氟化羰基化反应

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

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