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陈试剂(氟磺酰基二氟乙酸甲酯，FSO_2CF_2COOMe，全称为陈庆云试剂)是由我国科学家陈庆云院士课题组原创的实用高效的亲核三氟甲基化试剂。该试剂以四氟乙烯、三氧化硫、甲醇等廉价工业品为原料，可便捷实现规模化制备。该试剂凭借独特的分子骨架与多重活化路径，在有机氟化学、药物分子修饰及功能材料等领域展现出广阔的应用价值。近年来，围绕陈试剂骨架的衍生化、新反应开发、催化体系拓展及机理研究等持续取得突破。通过结构定向修饰，已经成功开发出铜盐、银盐、三甲基硅酯、磺酰氯及羧酸等系列衍生化试剂。这些衍生体系突破了单一亲核反应的局限，实现了从亲核三氟甲基化到自由基双官能团化、脱氧氟化、亲电氟烷基化、光催化转化等多类型的应用。基于上述进展，本文系统综述了陈试剂及其衍生物的发展脉络、结构特点、反应类型、作用机制及相关应用。重点梳理2020～2026年报道的新反应类型、新催化体系与新功能化应用场景，同时总结其在医药农药、功能高分子、电化学储能交叉领域的应用实例，剖析现有体系存在的局限，并对其发展方向进行展望。
Abstract：Chen's reagent(methyl fluorosulfonyl difluoroacetate,FSO_2CF_2COOMe,also known as Qingyun Chen' s reagent) is a practical and highly efficient nucleophilic trifluoromethylation reagent originally developed by Academician Chen Qingyun,a Chinese scientist.This reagent is readily scalable for large-scale production using inexpensive industrial raw materials such as tetrafluoroethylene,sulfur trioxide,and methanol. Thanks to its unique molecular framework and multiple activation pathways,it demonstrates broad application potential in fields such as organofluorine chemistry,drug molecule modification,and functional materials.In recent years,continuous breakthroughs have been achieved in the derivatization of the skeleton of Chen's reagent,the development of new reactions,the expansion of catalytic systems,and mechanistic studies.Through structure-directed modification,a series of derivatized reagents—including copper salts,silver salts,trimethylsilyl esters,sulfonyl chlorides,and carboxylic acids—have been successfully developed.These derivative systems have overcome the limitations of single nucleophilic reactions,enabling a wide range of applications,from nucleophilic trifluoromethylation to radical bifunctionalization,deoxyfluorination,electrophilic fluoroalkylation,and photocatalytic transformations. Based on these advances,this paper systematically reviews the development history,structural characteristics,reaction types,mechanisms of action,and relevant applications of Chen' s reagent and its derivatives.The review focuses on new reaction types,catalytic systems,and functionalization applications reported between 2020 and 2026. It also summarizes application examples from the interdisciplinary fields of pharmaceuticals,pesticides,functional polymers,and electrochemical energy storage,analyzes the limitations of existing systems,and outlines future development directions.
[1]Müller K, Faeh C, Diederich F. Science, 2007,317(5846):1881-1886.
[2]Inoue M,Sumii Y,Shibata N.ACS Omega,2020,5(19):10633-10640.
[3]Tomashenko O A,Grushin V V. Chem. Rev.,2011,111(8):4475-4521.
[4]Chen Q Y,Wu S W.J.Chem.Soc.,Chem.Commun.,1989,11:705-706.
[5]Chen Q Y.J.Fluor.Chem.,1995,72(2):241-246.
[6]Chen Q Y.Chin.J.Org.Chem.,2001,21(11):805-809.
[7]Zhang C P,Chen Q Y,Guo Y,Xiao J C,Gu Y C.Coord.Chem.Rev.,2014,261:28-72.
[8]Liu C,Guo Y,Xiao J C.Chem.Eur.J.,2024,10(1):7-18.
[9]Xie Q Q,Hu J B.Chin.J.Chem.Eur.J.,2020,38(2):202-212.
[10]Clarke S L,Mcglacken G P.Chem.Eur.J.,2017,23(6):1219-1230.
[11]Huang G L,Xue X S.Acta Chim.Sin.,2024,82(2):132-137.
[12]Zhao G,Wu H,Xiao Z W,Chen Q Y,Liu C.RSC Adv.,2016,6(55):50250-50254.
[13]Le B J,Wu H,Hu X J,Zhou X M,Guo Y,Chen Q Y,Liu C.Tetrahedron Lett.,2020,61(50):152624.
[14]Wu X,Qiu X,Lou W R,Zhang S X,Zhang C Y,Ma X Y,Liu C.Molecules,2024,29(12):2849.
[15]Liu Y A,Wu H,Guo Y,Xiao J C,Chen Q Y,Liu C.Angew.Chem.Int.Ed.,2017,56(48):15432-15435.
[16]Zhang H Z,Xiao W C,Wu F H,Ma X Y,Liu C.Sci.China Chem.,2025,68(5):1763-1778.
[17]Lin Q Z,Liu Y A,Xiao Z W,Zheng L P,Zhou X M,Guo Y,Chen Q Y,Zheng C G,Liu C. Org. Chem. Front.,2019,6(4):447-450.
[18]Zhang S,Xiao W,Wu J,Wu F,Huang H,Ma X,Shi Y,Liu C.Molecules,2024,29(23):5622.
[19]Tian F,Kruger V,Bautista O,Duan J X,Li A R,Dolbier W R,Chen Q Y.Org.Lett.,2000,2(4):563-564.
[20]Fuchibe K,Ichikawa J.Chem.Commun.,2023,59(18):2532-2540.
[21]Yamani K,Pierre H,Archambeau A,Meyer C,Cossy J.Angew.Chem.Int.Ed.,2020,59(42):18505-18509.
[22]Ma X S,Pinto W,Pham L N,Sloman D L,Han Y X.Eur.J.Org.Chem.,2020,2020(29):4581-4605.
[23]Tang H J,Shi X M,Zhu X Y,Wang C Q,Feng C.Chin.J.Chem.,2023,41(22):2981-2987.
[24]Fuchibe K,Miura T,Ichikawa J. Eur. J. Org. Chem.,2025,28(35):e202500586.
[25]Yuan W J,Shou J Y,Qing F L. Org. Lett.,2025,27(51):14276-14280.
[26]Sang X H,Wang J,Zhou J,Xu Y,An J,Warshel A,Huang Z W. J. Am. Chem. Soc.,2023,145(50):27248-27253.
[27]Levchenko K,Datsenko O P,Serhiichuk O,Tolmachev A,Iaroshenko V O,Mykhailiuk P K.J.Org.Chem.,2016,81(14):5803-5813.
[28]Cabrera P J,Allais C,Arcari J T,González-esguevillas M,Mcinturff E L,Reese M R. Org. Process Res. Dev.,2024,28(4):1119-1128.
[29]Sasaki I,Tada M,Liu Z Y,Tatsuta M,Okura T,Aoki M,Takahashi K,Ishioka N S,Watanabe S,Tanaka H. Org.Biomol.Chem.,2023,21(36):7467-7472.
[30]Thomoson C S,Tang X J,Dolbier W R. J. Org. Chem.,2015,80(2):1264-1268.
[31]Zheng L P,Qiu X,Xiao Z W,Ma X Y,Gao T Z,Zhou X M,Wang Y F,Guo Y,Chen Q Y,Liu C. J. Org. Chem.,2023,88(11):7518-7524.
[32]Panja C,Puttaramu J V,Chandran T K,Nimje R Y,Kumar H,Gupta A,Arunachalam P N,Corte J R,Mathur A.J.Fluor.Chem.,2020,236:109516.
[33]Yu W,Xu X H,Qing F L. Org. Lett.,2016,18(19):5130-5133.
[34]Luo X W,Zhang B,Xi C J.Green Chem.,2021,23(6):2324-2328.
[35]Zou S,Luo X W,Chen C,Xi C J. Org. Biomol. Chem.,2022,20(18):3726-3730.
[36]Hu J,Li S Y,Zheng S C,Zhao X M,Wang X L.Synthesis,2022,54(9):2282-2288.
[37]Maddess M L,Scott J P,Alorati A,Baxter C,Bremeyer N,Brewer S,Campos K,Cleator E,Dieguez-vazquez A,Gibb A,Gibson A,Howard M,Keen S,Klapars A,Lee J,Li J,Lynch J,Mullens P,Wallace D,Wilson R. Org.Process Res.Dev.,2014,18(4):528-538.
[38]Mangla P,Sanghvi Y S,Prasad A K.Curr.Protoc.,2021,1(12):e328.
[39]Ren J Z,Ji X,Zhang J,Yu Z W,Wang X Y,Xiong L X,Yang N,Tang L F,Li Z M,Fan Z J. J. Agric. Food Chem.,2024,72(14):8072-8080.
[40]Cai Y,Gu H F,Li L,Liu X,Bai Y,Shen L,Han B,Xu Y G,Yao H H.Pharmacol.Res.,2024,210:107508.
[41]Shen J,White N A,Tian Q P,Sirois L E,Zhang H M,Gosselin F.Org.Process Res.Dev.,2024,28(1):92-101.
[42]Song J,Aswar V R,Jarhad D B,Jeong L S. Org. Lett.,2025,27(9):2215-2219.
[43]Duan X Y,Wang J Q,Huo X G,Shen Z,Ding Y H.Eur.J.Med.Chem.,2025,286:117283.
[44]Zhang W,Lin J H,Wu W F,Cao Y C,Xiao J C.Chin.J.Chem.,2020,38(2):169-172.
[45]Stefanello F S,Kappenberg Y G,Araújo J N,Gritzenco F,Luz F M,Martins M A P,Zanatta N,Iglesias B A,Bonacorso H G.J.Mol.Struct.,2024,1311:138350.
[46]Kim S J,Jeong S,Byun T,Kim J S,Lee H,Kim S Y.Polymers,2025,17(3):309.
[47]Jangra R,Nair A J,Kuriakose A,Acharyya J N,Prakash G V,Sankar M. Dalton Trans.,2025,54(26):10234-10245.
[48]Jiao T P,Liu G P,Zou Y,Yang X R,Zhang X Z,Fu A,Zheng J M,Yang Y.J.Power Sources,2021,515:230618.
[49]Xiang F Y,Wang P P,Cheng H.Energy Technol.,2020,8(3):2000487.
[50]Liu Z W,Shi L F,Liu Y G,Ma C,Zhang G X,Li S,Zhao W,Du C Y,Huo H,Yin G P,Guo R,Ma Y L. J.Energy Chem.,2026,117:386-396.
[51]Huang H N,Huang L L,Chen S,Liao Y H,Li W S.J.Power Sources,2026,674:239741.
[52]Yang J,Hou J M,Fang Z X,Kashif K,Chen C,Li X R,Zhou H P,Zhang S,Feng T T,Xu Z Q,Wu M Q.Chem.Eng.J.,2022,433:133193.
[53]Wang X S,Wu J R,Zhao Y,Li B,Tavajohi N,Liu Q,Duan J G,Wang D,Dong P,Zhang Y J,Li B H.J.Energy Chem.,2023,82:287-295.
[54]Wang K,Wang C T,Liu S,Du C C,Zheng Q Y,Cui J Q,Yang X X,Tang Y X,Yuan R M,Zheng M S,Fan J M,Dong Q F. Energy Environ. Sci.,2025,18(5):2610-2621.
[55]Yang Z H,Qiu C,Chen H S,Hong Y,Shi K X,Liu Q B.J.Mater.Chem.A,2025,13(38):32504-32514.
[56]Shi C Y,Li Z G,Wang M R,Hong S,Hong B,Fu Y X,Liu D,Tan R,Wang P S,Lai Y Q.Energy Environ.Sci.,2025,18(7):3248-3258.
[57]Pan T,Yang P H,Zhang S Q,Guo Q P,Zheng C M,Liu S K,Li Y J,Sun W W. Adv. Funct. Mater.,2026,36(28):e27980.
[58]Zhou W,Liu G H,Mo Y B,Zhu X,Zhu K Y,Dong X L.Energy Environ.Sci.,2026,19(1):299-311.
[59]Liao Y Q,Liu H,Zhang Y Q,Yang J Y,Ji H J,Wang D H,Yuan L X,Huang Y H,Ren Y. ACS Nano,2025,19(33):30466-30475.
基本信息:
DOI：10.13822/j.cnki.hxsj.2026.0211
中图分类号:TQ421
引用信息:
[1]苏雪,丁婧,曾广原,等.陈试剂的研究进展:从亲核三氟甲基化试剂到多功能氟烷基化试剂[J].化学试剂,2026,48(10):10-24.DOI:10.13822/j.cnki.hxsj.2026.0211.
基金信息:
国家自然科学基金项目(22471172,21871283)
2026-08-20
2026
2026-09-15
2026-09-18
2026
1
2026-09-20
2026-09-20
2026-09-20