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DOI: https://doi.org/10.6023/cjoc202605004

综述与进展

芳基鋶盐的氟化和氟烷基化反应研究进展

  • 浮晓静 ,
  • 吴萍 ,
  • 宋佳威 ,
  • 辛鑫 ,
  • 徐文瑨 ,
  • 张成潘
展开
  • a武汉理工大学化学化工与生命科学学院 武汉 430070

收稿日期: 2026-05-07

  修回日期: 2026-06-06

  网络出版日期: 2026-07-14

基金资助

湖北省自然科学基金(No. 2024DJC038)资助项目.

收起

Progress on Fluorination and Fluoroalkylation Reactions of Aryl Sulfonium Salts

  • Fu Xiaojing ,
  • Wu Ping ,
  • Song Jiawei ,
  • Xin Xin ,
  • Xu Wenjin ,
  • Zhang Chengpan
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  • aSchool of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070

Received date: 2026-05-07

  Revised date: 2026-06-06

  Online published: 2026-07-14

Supported by

Natural Science Foundation of Hubei Province (No. 2024DJC038).

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摘要

芳基鋶盐因制备简单、结构多样、位点选择性好、反应性质丰富等优点,已成为芳烃精准官能团化的重要原料。近年来,芳基鋶盐在氟化及氟烷基化反应中得到了广泛应用,其中环状芳基鋶盐如噻蒽鋶盐、吩噁噻鋶盐、二苯并噻吩鋶盐和吩噻嗪鋶盐等尤为受到关注。本文全面总结了芳基鋶盐参与的氟化和氟烷基化反应,主要分为以下三类：1）Ar-F键与Ar-[18F]键的构建,包括过渡金属和可见光协同催化的氟化反应、以及放射性[18F]标记的芳香亲核取代反应;2）Ar-CF2H键、Ar-CF2COR键、Ar-CF3键和Ar-CF(CF3)2键的构建,涵盖过渡金属催化的偶联、无催化剂参与的偶联、以及光诱导的自由基偶联等;3）Ar-OCF3键、Ar-SCF3键、Ar-SeCF3键及Ar-TeCF3键的构建,涉及的反应机理包括过渡金属催化、机械化学转化、以及光催化电子供体-受体（EDA）复合物活化等。这些反应为芳基鋶盐在氟化学中的进一步应用提供了重要参考。

关键词： 芳基鋶盐; 氟化; [18F]标记; 氟烷基化

本文引用格式

浮晓静 , 吴萍 , 宋佳威 , 辛鑫 , 徐文瑨 , 张成潘 . 芳基鋶盐的氟化和氟烷基化反应研究进展[J]. 有机化学, 0 : 202605004 -202605004 . DOI: 10.6023/cjoc202605004

Abstract

Aryl sulfonium salts have exhibited obvious advantages such as simple preparation, structural diversity, good site-selectivity, and rich reactivity, and have emerged as important intermediates for the precise functionalization of arenes. In recent years, aryl sulfonium salts have been widely utilized in fluorination and fluoroalkylation reactions, among which cyclic aryl sulfonium salts such as thianthrenium, phenoxathiinium, dibenzothiophenium, and phenothiazinium salts have attracted particular attention. This article comprehensively summarizes the progress on fluorination and fluoroalkylation reactions of aryl sulfonium salts, which are mainly categorized into three types: 1) Construction of Ar-F and Ar-[18F] bonds via transition-metal- and visible-light-catalyzed fluorination and aromatic nucleophilic substitution with radioactive [18F] salts; 2) Formation of Ar-CF2H, Ar-CF2COR, Ar-CF3, and Ar-CF(CF3)2 bonds through transition-metal-catalyzed couplings, catalyst-free coupling, and photoinduced radical couplings; 3) Construction of Ar-OCF3, Ar-SCF3, Ar-SeCF3, and Ar-TeCF3 bonds, involving reaction mechanisms such as transition-metal catalysis, mechanochemical transformation, and photocatalytic activation of electron donor-acceptor (EDA) complexes. These reactions provide important references for the further application of aryl sulfonium salts in fluorine chemistry.

Key words： aryl sulfonium salts; fluorination; [18F]-labeling; fluoroalkylation

参考文献

[1] (a) Grygorenko O. O.; Melnykov K. P.; Holovach S.; Demchuk O. ChemMedChem2022, 17, e202200365.
(b) Wang Y.-Z.; Ming X.-X.; Zhang, C.-P. Curr. Med. Chem. 2020, 27, 5599.
(c) Meanwell, N. A. J. Med. Chem. 2018, 61, 5822.
(d) Inoue M.; Sumii Y.; Shibata N. ACS Omega2020, 5, 10633.
(e) Du Y.; Bian Y.; Baecker D.; Dhawan G.; Semghouli A.; Kiss L.; Zhang W.; Sorochinsky A. E.; Soloshonok V. A.; Han, J. Chem. Eur. J. 2025, 31, e202500662.
[2] (a) Jeschke, P.Pest Manag. Sci. 2024, 80, 3065.
(b) Wang Q.; Song H.; Wang, Q. Chin. Chem. Lett. 2022, 33, 626.
[3] (a) Zhang C.; Yan K.; Fu C.-K.; Peng H.; Hawker C. J.; Whittaker, A. K. Chem. Rev. 2022, 122, 167.
(b) Koguchi R.; Jankova K.; Tanaka M. Acta Biomater. 2022, 138, 34.
[4] (a) O’Hagan, D. Chem. Soc. Rev. 2008, 37, 308.
(b) Lowe P. T.; O’Hagan, D. J. Fluorine Chem. 2020, 230, 109420.
(c) Zhou Y.; Wang J.; Gu Z.-N.; Wang S.-N.; Zhu W.; Aceña J. L.; Soloshonok V. A.; Izawa K.; Liu H. Chem. Rev. 2016, 116, 422.
[5] (a) Barata-Vallejo S.; Bonesi S. M.; Postigo A. ACS Catal. 2024, 14, 15879.
(b) See Y. Y.; Morales-Colon M. T.; Bland D. C.; Sanford, M. S. Acc. Chem. Res. 2020, 53, 2372.
(c) Szpera R.; Moseley D. F. J.; Smith L. B.; Sterling A. J.; Gouverneur, V. Angew. Chem. Int. Ed. 2019, 58, 14824.
(d) Cahard D.; Ma, J.-A. Emerging Fluorinated Motifs: Synthesis, Properties, and Applications,2020 Wiley-VCH Verlag GmbH & Co. KGaA.
[6] (a) Yamamoto K.; Li J.; Garber J. A. O.; Rolfes J. D.; Boursalian G. B.; Borghs J. C.; Genicot C.; Jacq J.; van Gastel M.; Neese F.; Ritter T. Nature2018, 554, 511.
(b) Barata-Vallejo S.; Bonesi S. M.; Postigo A. RSC Adv. 2015, 5, 62498.
(c) Baguia H.; Evano, G. Chem. Eur. J. 2022, 28, e202200975.
[7] (a) Tian Z.-Y.; Hu Y.-T.; Teng H.-B.; Zhang C.-P. Tetrahedron Lett. 2018, 59, 299.
(b) Kozhushkov, S. I.; Alcarazo, M.Eur. J. Inorg. Chem. 2020, 2486.
(c) Fan R.; Tan C.; Liu Y.-G.; Wei Y.; Zhao X.-W.; Liu X.-Y.; Tan J.-J.; Yoshida, H. Chin. Chem. Lett. 2021, 32, 299.
(d) Yorimitsu, H. Chem. Rec. 2021, 21, 3356.
(e) Tian Z.-Y.; Ma Y.; Zhang C.-P. Synthesis2022, 54, 1478.
(f) van Dalsen L.; Brown R. E.; Rossi-Ashton J. A.; Procter, D. J. Angew. Chem. Int. Ed. 2023, 62, e202303104.
(g) Timmann S.; Feng Z.-Y.; Alcarazo, M. Chem. Eur. J. 2024, 30, e202402768.
(h) Bai Z.-B.; Ritter, T. Acc. Chem. Res. 2026, 59, 915.
(i) Wu X.-Y.; Gao P.; Chen, F. Eur. J. Org. Chem. 2023, 26, e202300864.
(j) Pohorenec R. A.; Xu, S.-Q. Org. Chem. Front. 2026, 13, 1424.
(k) Chen X.-Y.; Wu Y.; Wang P. Synthesis2022, 54, 3928.
(l) Xu H.; Zhang J.; Zuo J.; Wang F.; Lü J.; Hun X.; Yang, D. Chin. J. Org. Chem. 2022, 42, 4037 (in Chinese).
(徐浩, 张杰, 左峻泽, 王丰晓, 吕健, 混旭, 杨道山, 有机化学, 2022, 42, 4037).
(m) Song, J.-W.; Han, X.; Zhang, C.-P.Chem. Rec. 2026, e70172.
[8] (a) Sekar G.; Nair V. V.; Zhu, J.-P. Chem. Soc. Rev. 2024, 53, 586.
(b) Mahmudov K. T.; Kopylovich M. N.; Guedes da Silva, M. F. C.; Pombeiro, A. J. L. Dalton Trans. 2017, 46, 10121.
[9] (a) Crivello J. V.; Lam, J. H. W. J. Org. Chem.1978, 43, 3055.
(b) Boduszek B.; Shine, H. J. J. Org. Chem.1988, 53, 5142.
(c) Yamamoto, K.; Miyatake, K.; Nishimura, Y.; Tsuchida, E.Chem. Commun. 1996, 2099.
(d) Racicot L.; Kasahara T.; Ciufolini, M. A. Org. Lett. 2014, 16, 6382.
(e) Berger, F.; Plutschack, M. B.; Riegger, J.; Yu, W.-W.; Speicher, S.; Ho, M.; Frank, N.; Ritter, T.Nature 2019, 567, 223.
(f) Wu J.; Wang Z.-W.; Chen X.-Y.; Wu Y.-C.; Wang D.-M.; Peng Q.; Wang, P. Sci. China Chem. 2020, 63, 336.
(g) Kafuta, K.; Korzun, A.; Böhm, M.; Golz, C.; Alcarazo, M.Angew. Chem. Int. Ed. 2020, 59, 1950.
(h) Chen X.-Y.; Li Y.-N.; Wu Y.-C.; Bai J.-H.; Guo Y.-L.; Wang, P. J. Am. Chem. Soc. 2023, 145, 10431.
(i) He Z.; Dydio, P. Angew. Chem. Int. Ed. 2024, 63, e202410616.
(j) Guan Y.-H.; Peng X.; Fan R.; Feng X.-Y.; Du H.-G.; Tan, J.-J. Chin. Chem. Lett. 2026, 37, 111132.
(k) Roberts R. A.; Herkemij P.; Damle H.; Stuart, D. R. Org. Lett. 2026, 28, 438.
(l) Brown R. E.; Kaur N.; Nassoy A. C. M. A.; Romano C.; Procter, D. J. Angew. Chem. Int. Ed. 2026, 65, e202525298.
[10] (a) Yoshida T.; Honda Y.; Morofuji T.; Kano N. Org. Lett. 2021, 23, 9664.
(b) Yoshida T.; Honda Y.; Morofuji T.; Kano, N. J. Org. Chem. 2022, 87, 7565.
(c) Yao Y.-F.; Song J.-W.; Zhang, C.-P. Org. Biomol. Chem. 2024, 22, 7866.
[11] Campbell M. G.; Ritter T. Chem. Rev. 2015, 115, 612.
[12] Li J.-K.; Chen J.-T.; Sang R.-C.; Ham W.-S.; Plutschack M. B.; Berger F.; Chabbra S.; Schnegg A.; Genicot C.; Ritter T.Nat. Chem. 2020, 12, 56.
[13] (a) Miller P. W.; Long N. J.; Vilar R.; Gee, A. D. Angew. Chem. Int. Ed. 2008, 47, 8998.
(b) Tredwell M.; Gouverneur, V. Angew. Chem. Int. Ed. 2012, 51, 11426.
(c) Zhu Y.; Chen L.; Hou W.; Li, Y. Chin. J. Org. Chem. 2021, 41, 1774 (in Chinese).
(朱源, 陈乐园, 侯文彬, 李祎亮, 有机化学, 2021, 41, 1774).
(d) Chen H.; Zhang B.; Chen S.; Xiong F.; Zhu X.; Yu B.; Long S. Bioorg. Chem. 2025, 157, 108272.
[14] Mu L.-J.; Fischer C. R.; Holland J. P.; Becaud J.; Schubiger P. A.; Schibli R.; Ametamey S. M.; Graham K.; Stellfeld T.; Dinkelborg L. M.; Lehmann L.Eur. J. Org. Chem. 2012, 889.
[15] Sander K.; Gendron T.; Yiannaki E.; Cybulska K.; Kalber T. L.; Lythgoe M. F.; Årstad E. Sci. Rep. 2015, 5, 9941.
[16] Gendron T.; Sander K.; Cybulska K.; Benhamou L.; Sin P. K. B.; Khan A.; Wood M.; Porter M. J.; Årstad, E. J. Am. Chem. Soc. 2018, 140, 11125.
[17] Xu P.; Zhao D.; Berger F.; Hamad A.; Rickmeier J.; Petzold R.; Kondratiuk M.; Bohdan K.; Ritter T.Angew. Chem. Int. Ed. 2020, 59, 1956.
[18] (a) Zafrani Y.; Yeffet D.; Sod-Moriah G.; Berliner A.; Amir D.; Marciano D.; Gershonov E.; Saphier, S. J. Med. Chem. 2017, 60, 797.
(b) Sap J. B. I.; Meyer C. F.; Straathof N. J. W.; Iwumene N.; am Ende C. W.; Trabanco A. A.; Gouverneur, V. Chem. Soc. Rev. 2021, 50, 8214.
(c) Carvalho D. R.; Christian, A. H. Org. Biomol. Chem. 2021, 19, 947.
(d) Ding X.; Yao Y.-F.; Lin W.; Ye Z.; Zhang, C.-P. J. Fluorine Chem. 2024, 273, 110238.
[19] Ye F.; Berger F.; Jia H.; Ford J.; Wortman A.; Börgel J.; Genicot C.; Ritter, T. Angew. Chem. Int. Ed. 2019, 58, 14615.
[20] Jiang X.-J.; Gong W.-B.; Li X.-X.; Wang S.-T.; Gu Z.-Y.; Yang Y.-H.; Zeng X.-J.ACS Catal. 2024, 14, 13557.
[21] Du Z.-B.; Gong W.-B.; Yuan S.-L.; Ren Y.-F.; Huang C.-T.; Zeng X.-J. Org. Lett. 2024, 26, 11062.
[22] Ahmadli D.; Müller S.; Xie Y.-H.; Smejkal T.; Jaeckh S.; Iosub A. V.; Williams S. R.; Ritter, T. J. Am. Chem. Soc. 2025, 147, 4268.
[23] Yang J.; Song J.-W.; Zhang C.-P. Org. Lett. 2026, 28, 1101.
[24] Xia F.; Wang Y.-H.; Ding X.-Y.; Zhang, C.-P. Chem. Asian J. 2025, 20, e202500331.
[25] (a) Novás, M.; Matos, M. [J] .Molecules 2025, 30, 3009.
(b) He W.; Yi R.; Yang Z.; Wu Z.; He, W. Chin. J. Org. Chem. 2025, 45, 3534 (in Chinese).
(何卫保, 易荣楠, 杨梓, 伍智林, 何卫民, 有机化学, 2025, 45, 3534).
(c) Xiao H.; Zhang Z.; Fang Y.; Zhu L.; Li, C. Chem. Soc. Rev. 2021, 50, 6308.
(d) Chen D.; Jiang J.; Wan, J.-P. Chin. J. Chem. 2022, 40, 2582.
(e) Han Z.-Z.; Zhang, C.-P. Adv. Synth. Catal. 2020, 362, 4256.
(f) Mandal D.; Maji S.; Pal T.; Sinha S. K.; Maiti D. Chem. Commun. 2022, 58, 10442.
[26] Yang X.-Y.; Wang J.-M.; Pei M.-Y.; Wang S.-Y.; Shang R.; Wei X.-F. Org. Lett. 2024, 26, 10934.
[27] Yang Y.-F.; Zhao L.-L.; Luo S.-S.; Jiang X.-J.; Yuan Y.-L.; Zeng X.-J. Chem. Commun. 2026, 62, 8270.
[28] Xu M.-Z.; Xiao F.-Y.; Gu Y.-C.; Shu T.; Zhang C.-P. Org. Lett. 2025, 27, 13621.
[29] Veth L.; Windhorst A. D.; Vugts D. J.Angew. Chem. Int. Ed. 2026, e202525709.
[30] (a) Sheppard, W. A. J. Am. Chem. Soc.1965, 87, 2410.
(b) Hansch C.; Leo A.; Taft, R. W. Chem. Rev.1991, 91, 165.
(c) Chen Y.-W.; Li Y.-X.; Pan L.; Liu J.-B.; Wan Y.-Y.; Chen W.; Xiong L.-X.; Yang N.; Song H.-B.; Li, Z.-M. Bioorg. Med. Chem. 2014, 22, 6366.
(d) Tohnishi M.; Nakao H.; Furuya T.; Seo A.; Kodama H.; Tsubata K.; Fujioka S.; Kodama H.; Hirooka T.; Nishimatsu, T. J. Pestic. Sci. 2005, 30, 354.
(e) Nakao T.; Banba, S. Bioorg. Med. Chem. 2016, 24, 372.
(f) Liu D.; Ye J.; Gao Y.; Pei H.; Luo C.; Tian H.; He J.; Zhang J.; Zhang, L. J. Agric. Food Chem. 2024, 72, 15276.
[31] Li J.-Y.; Zhang C.-P.Org. Lett. 2026, 28, 2148.
[32] (a) Hao B.-Y.; Han Y.-P.; Zhang Y.-C.; Liang, Y.-M. Org. Biomol. Chem. 2023, 21, 4926.
(b) Si, Y.-F.; Tang, P.Chin. J. Chem. 2023, 41, 2179.
(c) Barata-Vallejo S.; Bonesi S. M.; Postigo, A. Chem. Eur. J. 2022, 28, e202201776.
(d) Ran, L.-Y.; Zhang, C.-P.Chin. J. Org. Chem. 2022, 42, 2045 (in Chinese).
(冉龙玉, 张成潘, 有机化学, 2022, 42, 2045).
[33] Mkrtchyan S.; Purohit V. B.; Zapletal J.; Shalimov O.; Nociarová J.; Addová G.; Filo J.; Garcia M. G.; Kupcová E.; Benická B.; Iaroshenko, V. O. Cell Rep. Phys. Sci. 2024, 5, 102118.
[34] (a) Li F.; Song J.-W.; Han X.; Zhang C.-P. Synthesis2025, 57, 539.
(b) Shen, Q. J. Org. Chem. 2023, 88, 3359.
(c) Wang X.; Wang Z.; Li Z.; Sun, K. Chin. Chem. Lett. 2023, 34, 108045.
(d) Huang Y.; Zhang M.; Lin Q.; Weng Z. Synlett2021, 32, 109.
[35] Chen J.-T.; Li J.-K.; Plutschack M. B.; Berger F.; Ritter, T. Angew. Chem. Int. Ed. 2020, 59, 5616.
[36] (a) Tlili A.; Ismalaj E.; Glenadel Q.; Ghiazza C.; Billard, T. Chem. Eur. J. 2018, 24, 3659.
(b) Wang H.-N.; Dong J.-Y.; Shi J.; Zhang C.-P. Tetrahedron2021, 99, 132476.
(c) Yang X.-H.; Chang D.; Zhao R.; Shi, L. Asian J. Org. Chem. 2021, 10, 61.
(d) Wang Y.; Ye Z.; Zhang H.; Yuan, Z. Adv. Synth. Catal. 2021, 363, 1835.
(e) Xiao, F.-Y.; Zhang, C.-P.Organomet. Chem. 2025, 46, 157.
[37] Tian Z.-Y.; Zhang, C.-P. Org. Chem. Front. 2022, 9, 2220.
[38] (a) Grollier, K.; Taponard, A.; Billard, T.Eur. J. Org. Chem. 2020, 6943.
(b) Sperger T.; Guven S.; Schoenebeck, F. Angew. Chem. Int. Ed. 2018, 57, 16903.
(c) Dong J.-Y.; Wang H.-N.; Xie Y.-Q.; Zhang C.-P. iScience 2022, 25, 105566.
(d) Dong J.-Y.; Wang H.-N.; Zhang C.-P. ChemistrySelect2023, 8, e202302350.
[39] Guan P.-Y.; Li F.; Han L.-J.; Yu Y.; Zhang, C.-P. Org. Chem. Front. 2025, 12, 3579.
[40] (a) Mato M.; Rivas-Saborido A.; Casas-Pais A.; Tomás-Gamasa M.; Mascareñas, J. L. J. Am. Chem. Soc. 2026, 148, 5946.
(b) Bohdan K.; Hartmann P.; Müller S.; Marchionni D.; Preisinger C.; Jacobs J. B.; Vogelsang L.; Sterling M. S.; Dietz K.-J.; Ritter, T. J. Am. Chem. Soc. 2025, 147, 45576.
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