综述与进展

可见光诱导三氟甲基化研究进展:三氟乙酸与三氟乙酸酐作为廉价高效的三氟甲基化试剂

  • 黄斌 ,
  • 许展图 ,
  • 陈静 ,
  • 苏伟平 ,
  • 朱晨
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  • a福州大学化学学院 福建福州 350108
    b中国科学院福建物质结构研究所 结构化学全国重点实验室 福建福州 350108
    c变革性分子前沿科学中心 上海市手性药物分子工程重点实验室 上海交通大学 上海 200240

收稿日期: 2026-03-06

  修回日期: 2026-05-09

  网络出版日期: 2026-06-18

Advances in Visible-Light Induced Trifluoromethylation with Trifluoroacetic Acid and Its Anhydride as Inexpensive and Effective Trifluoromethylation Reagents

  • Bin Huang ,
  • Zhantu Xu ,
  • Jing Chen ,
  • Weiping Su ,
  • Chen Zhu
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  • aCollege of Chemistry, Fuzhou University, Fuzhou, Fujian 350108
    bState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350108
    cFrontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, Shanghai 200240

Received date: 2026-03-06

  Revised date: 2026-05-09

  Online published: 2026-06-18

摘要

三氟甲基在医药、农药和材料科学多方面的重要作用,推动了三氟甲基化合成方法及三氟甲基试剂的研发。可见光催化的三氟甲基化作为一种绿色高性能的合成策略,已成为构建含三氟甲基分子的重要手段,展现出广阔的应用前景。本文围绕廉价高效的三氟甲基试剂三氟乙酸及三氟乙酸酐在可见光条件下的活化转化,从预合成中间体活化、由活化试剂原位活化和直接活化三个方向,系统评述了近十年该领域的研究进展,梳理其发展历程,阐述活化方式、反应机制及转化类型等关键科学问题,旨在为该领域未来催化策略的理性设计提供参考。

本文引用格式

黄斌 , 许展图 , 陈静 , 苏伟平 , 朱晨 . 可见光诱导三氟甲基化研究进展:三氟乙酸与三氟乙酸酐作为廉价高效的三氟甲基化试剂[J]. 有机化学, 0 : 3009 . DOI: 10.6023/cjoc202603009

Abstract

The trifluoromethyl group plays a crucial role in pharmaceuticals, agrochemicals, and materials science, driving extensive efforts in the discoveries of new trifluoromethylating reagents and the development of methods for introducing this group into molecular frameworks. Over the past decade, the field of visible-light photocatalysis has flourished. Visible-light photocatalytic trifluoromethylation, as a green and efficient synthetic strategy, has emerged as an important method for constructing trifluoromethyl-containing molecules with broad application prospects. This article systematically reviews the research progress of exploring on trifluoroacetic acid and its anhydride as inexpensive and effective trifluoromethyl reagents for visible-light catalyzed trifluoromethylation reactions. It focuses on key scientific issues such as activating methods, reaction mechanisms, and transformations. The insights gained are expected to facilitate the rational design of effective photocatalytic strategies for future utilization of trifluoroacetic acid or its anhydride.

参考文献

[1] Alonso C.;de Marigorta, E. M.;Rubiales, G.;Palacios, F.Chem. Rev. 2015, 115, 1847.
[2] Purser S.;Moore P. R.;Swallow S.;Gouverneur V.Chem. Soc. Rev. 2008, 37, 320.
[3] Zhang J.;Jin C. F.;Zhang Y. J.Chin. J. Org. Chem. 2014, 34, 662.
[4] K. Müller, C. F., F. DiederichScience 2007, 317, 1881.
[5] Qing F. L.;Liu X. Y.;Ma J. A.;Shen Q. L.;Song Q. L.;Tang P. P.CCS Chem. 2022, 4, 2518.
[6] Liu M. J.;Cai Y. L.;Shi R. C.;He Y. M.;He P. P.;Sun Y. J.;Gao X. F.;Hong L. C.;Yao S. Y.;Bao Z. B.;Yang Q. W.;Ren Q. L.;Zhang Z. G.Sci. Sin. Chim 2025, 55, 2828.
[7] Koike T.Asian J. Org. Chem. 2020, 9, 529.
[8] Li M.;Xue X. S.;Cheng J. P.Acc. Chem. Res. 2020, 53, 182.
[9] Jia H.;Haring A. P.;Berger F.;Zhang L.;Ritter T.J. Am. Chem. Soc. 2021, 143, 7623.
[10] Liu S.;Zhou J.;Yu L.;Liu Y. L.;Huang Y. G.;Ouyang Y.;Liu G. K.;Xu X. H.;Shibata N.Chem. Rev. 2025, 125, 4603.
[11] He W. M.;Wu Z. L.;Yang Z.;Yi R. N.;He W. B.Chin. J. Org. Chem. 2025, 45, 3534.
[12] Tan F. F.;Li Z. C.Front. Chem. 2025, 13, doi: 10.3389/fchem.2025.1602003.
[13] Tamaki S.;Kusamoto T.;Tsurugi H.Chemcatchem 2025, 17, e202402106.
[14] Lin J.;Li Z.;Kan J.;Huang S. J.;Su W. P.;Li Y. D.Nat. Commun. 2017, 8, 14353.
[15] Chen Y. X.;He Y. C.;Gao Y.;Xue J. K.;Qu W.;Xuan J.;Mo Y. M.Scienece 2024, 384, 670.
[16] Qi J.;Xu J. H.;Ang H. T.;Wang B. B.;Gupta N. K.;Dubbaka S. R.;O’Neill, P.;Mao, X. W.;Lum, Y. W.;Wu, J.J. Am. Chem. Soc. 2023, 145, 24965.
[17] Motornov V.;Trienes S.;Resta S.;Oliveira J. C.A.;Lin, Z. P.;Liu, Z.;von Münchow, T.;Stückl, C.;Ackermann, L.Angew. Chem. Int. Ed. 2025, 64, e202504143.
[18] Liang T.;Neumann C. N.;Ritter T.Angew. Chem. Int. Ed. 2013, 52, 8214.
[19] Studer A.Angew. Chem. Int. Ed. 2012, 51, 8950
[20] Garwood J. J.A.;Chen, A. D.;Nagib, D. A.J. Am. Chem. Soc. 2024, 146, 28034.
[21] Xiao H. W.;Zhang Z. Z.;Fang Y. W.;Zhu L.;Li C. Z.Chem. Soc. Rev. 2021, 50, 6308.
[22] Li L.;Mu X.;Liu W.;Wang Y.;Mi Z.;Li C. J.J. Am. Chem. Soc. 2016, 138, 5809.
[23] Lu B.;Zhang Z. H.;Jiang M.;Liang D.;He Z. W.;Bao F. S.;Xiao W. J.;Chen J. R.Angew. Chem. Int. Ed. 2023, 62, e202309460.
[24] Wu S.;Wu X. X.;Wang D.;Zhu C.Angew. Chem. Int. Ed. 2019, 58, 1499.
[25] Zhang Z. Z.;Zhu L.;Li C. Z.Chin. J. Chem. 2019, 37, 452.
[26] Xu P.;Fan W. Z.;Chen P. H.;Liu G. S.J. Am. Chem. Soc. 2022, 144, 13468.
[27] Li Z. L.;Li C. Y.;Ding Y.;Huo H. H.Coord. Chem. Rev. 2022, 460.
[28] Gu Q. S.;Li Z. L.;Liu X. Y.Acc. Chem. Res. 2020, 53, 170.
[29] Song L. L.;Cai L. C.;Gong L.;Van der Eycken, E. V.Chem. Soc. Rev. 2023, 52, 2358.
[30] Lin J. S.;Dong X. Y.;Li T. T.;Jiang N. C.;Tan B.;Liu X. Y.J. Am. Chem. Soc. 2016, 138, 9357.
[31] Depecker C.;Marzouk H.;Trevin S.;Devynckb J.New J. Chem. 1999, 23, 739.
[32] Zhang W. G.;Zou Z. L.;Wang Y. H.;Wang Y.;Liang Y.;Wu Z. G.;Zheng Y. X.;Pan Y.Angew. Chem. Int. Ed. 2019, 58, 624.
[33] Wu X. X.;Zhu C.Acc. Chem. Res. 2020, 53, 1620.
[34] Majhi J.;Dhungana R. K.;Renteria-Gomez, A.;Sharique, M.;Li, L. B.;Dong, W. Z.;Gutierrez, O.;Molander, G. A.J. Am. Chem. Soc. 2022, 144, 15871.
[35] Patra T.;Bellotti P.;Strieth-Kalthoff, F.;Glorius, F.Angew. Chem. Int. Ed. 2020, 59, 3172.
[36] Zheng Y.;Liao Z. H.;Xie Z. Z.;Chen H. B.;Chen K.;Xiang H. Y.;Yang H.Org. Lett. 2023, 25, 2129.
[37] Zhang W. G.;Zou Z. L.;Zhao W. X.;Lu S.;Wu Z. G.;Huang M. J.;Wang X. C.;Wang Y.;Liang Y.;Zhu Y.;Zheng Y. X.;Pan Y.Nat. Commun. 2020, 11, 2572.
[38] Huang M. J.;Ma J. W.;Zou Z. L.;Li H. Y.;Liu J. Y.;Kong L. Y.;Pan Y.;Zhang W. G.;Liang Y.;Wang Y.Chem. Sci. 2022, 13, 11312.
[39] Zhang M.;Lin J.-H.;Xiao J.-C.Org. Lett. 2021, 23, 6079.
[40] Wang Z.;Lin J. H.;Xiao J. C.Org. Lett. 2024, 26, 1980.
[41] Yang B.;Yu D. H.;Xu X. H.;Qing F. L.ACS Catal. 2018, 8, 2839.
[42] Kuehl N. J.;Taylor M. T.J. Am. Chem. Soc. 2023, 145, 22878.
[43] Rustin G. J.;Agarwal V.;Dalton P. I.;Jiang Z. H.;Liu Z.;Najor I. G.;Heydari B.;Heydari B.;Kuehl N. J.;Kumirov V.;Taylor M. T.;Gustafson J. L.Org. Lett. 2025, 27, 13504.
[44] Beatty J. W.;Douglas J. J.;Cole K. P.;Stephenson C. R.Nat. Commun. 2015, 6, 7919.
[45] Lewis S. E.;Wilhelmy B. E.;Leibfarth F. A.Chem. Sci. 2019, 10, 6270.
[46] Qi X. K.;Zhang H.;Pan Z. T.;Liang R. B.;Zhu C. M.;Li J. H.;Tong Q. X.;Gao X. W.;Wu L. Z.;Zhong J. J.Chem. Commun. 2019, 55, 10848.
[47] Ravetz B. D.;Tay N. E.S.;Joe, C. L.;Sezen-Edmonds, M.;Schmidt, M. A.;Tan, Y. C.;Janey, J. M.;Eastgate, M. D.;Rovis, T.ACS Cent. Sci. 2020, 6, 2053.
[48] McClain, E. J.;Monos, T. M.;Mori, M.;Beatty, J. W.;Stephenson, C. R. J.ACS Catal. 2020, 10, 12636.
[49] Hu Q.;Yu W. L.;Luo Y. C.;Hu X. Q.;Xu P. F.J. Org. Chem. 2022, 87, 1493.
[50] Zhang M.;Chen J.;Huang S. J.;Xu B. P.;Lin J.;Su W. P.Chem Catal. 2022, 2, 1793.
[51] Yin D. H.;Su D. Q.;Jin J.Cell Rep. Phys. Sci. 2020, 1, 100141.
[52] Ouyang Y.;Xu X. H.;Qing F. L.Angew. Chem. Int. Ed. 2018, 57, 1.
[53] Ouyang Y.;Xu X. H.;Qing F. L.Angew. Chem. Int. Ed. 2019, 58, 18508.
[54] Lee K.;Lee S.;Kim N.;Kim S.;Hong S.Angew. Chem. Int. Ed. 2020, 59, 13379.
[55] Zhang K.;Rombach D.;Notel N. Y.;Jeschke G.;Katayev D.Angew. Chem. Int. Ed. 2021, 60, 22487.
[56] Song Y.;Zheng B. H.;Yang S.;Li Y. F.;Liu Q.;Pan L.Org. Lett. 2023, 25, 2372.
[57] Zou L. Q.;Zhao H. Y.;Wang X. M.;Dong J.;Yang C. G.;Sun W. Q.;Xu J. B.;Fan B. M.Eur. J. Org. Chem. 2024, 27.
[58] Yang Y. Y.;Huang X. X.;Jin Y.Chem. Commun. 2025, 61, 1944.
[59] Juliá F.Chemcatchem 2022, 14, e202200916.
[60] Poznyak A. L.;Pavlovski V. I.Angew. Chem. Int. Ed. 1988, 27, 789.
[61] Jiang X. Y.;Lan Y.;Hao Y. D.;Jiang K.;He J.;Zhu J.;Jia S. Q.;Song J. S.;Li S. J.;Niu L. B.Nat. Commun. 2024, 15, 6115.
[62] Han W. R.;Zhao Z. Y.;Jiang K.;Lan Y.;Yu X. H.;Jiang X. Y.;Yang W.;Wei D. H.;Li S. J.;Niu L. B.Chem. Sci. 2024, 15, 19936.
[63] Song Z. H.;Guo L.;Yang C.;Xia W. J.Org. Chem. Front. 2024, 11, 4436.
[64] Fernández‐García, S.;Chantzakou, V. O.;Juliá‐Hernández, F.Angew. Chem. Int. Ed. 2023, 63, e202311984.
[65] Campbell B. M.;Gordon J. B.;Raguram E. R.;Gonzalez M. I.;Reynolds K. G.;Nava M.;Nocera D. G.Science 2024, 383, 279.
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