水相中的自由基反应研究进展

doi:10.6023/cjoc202512028

摘要/Abstract

自由基在化学反应中具有高反应活性和独特的选择性等特点,是构建复杂分子骨架的重要反应中间体。然而,传统的自由基反应严重依赖有毒、易挥发、易燃的有机溶剂。而水作为一种无毒、不可燃、廉价易得且对环境友好的绿色溶剂,发展以水为溶剂的自由基反应,为突破传统自由基反应的局限性提供了很好的解决方案,是当前绿色化学领域的一个前沿焦点。本文主要总结了2020-2025年间以水为溶剂的自由基反应研究进展,按照水相中的不同反应类型进行分类介绍,主要有以下几类：1、C-H/C-C键氧化反应;2、偶联反应;3、烯烃/炔烃自由基加成反应;4、其他类型反应。

关键词: 水相反应, 自由基, 绿色化学

Free radicals always serve as significant reaction intermediates for constructing complex molecular frameworks,which characterized by high reactivity and special selectivity in organic synthesis. However,traditional radical reactions heavily rely on toxic,volatile and inflammable organic solvents. Meanwhile,taking advantage of the properties of water,such as non-toxic,non-flammable,cheap,accessible and eco-friendly,developing aqueous phase radical reactions offers an excellent solution to overcome these limitations. The above is the frontier focus in green chemistry currently. This review mainly summarizes the research advances on radical reactions in aqueous phase between 2020 and 2025, which are categorized into: (1)C-H /C-C bond oxidation reactions; (2) coupling reactions; (3) radical additions to alkenes/alkynes; (4) other reactions.

Key words: aqueous reactions, radicals, green chemistry

引用此文

王小曼, 王泽, 吴劼, 胡燚, 叶盛青. 水相中的自由基反应研究进展[J]. 有机化学, doi: 10.6023/cjoc202512028.

Xiaoman Wang, Ze Wang, Jie Wu, Yi Hu, Shengqing Ye. Research Advances on Radical Reactions in Aqueous Phase[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202512028.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Gomberg, M. J. Am. Chem. Soc.1900, 22, 757.
[2] Yan M.; Lo J. C.; Edwards J. T.; Baran, P. S. J. Am. Chem. Soc.2016, 138, 12692.
[3] (a) Gao, S.-H.; Qiu, Y.-Y. Sci China Chem, 2016, 59, 1093.
(b) Xia, Q.; Dong, J.-Y.; Song, H.-J.; Wang, Q.-M. Chem. Eur. J. 2019, 25, 2949.
(c) Zhao, J.-P.; Ding, L.-J.; Wang, P.-C.; Liu, Y.; Huang, M.-J.; Zhou, X.-L.; Lu, M. Adv. Synth. Catal. 2020, 362, 5036.
(d) Hou, L.-Z.; Zhou, Y.-Q.; Yu, H.; Zhan, T.-Y.; Cao, W.-D.; Feng, X.-M. J. Am. Chem. Soc. 2022, 144, 22140.
(e) Ren, L.-Q.; Li, N.; Ke, J.; He, C. Org. Chem. Front. 2022, 9, 6400.
(f) Hu, Z.-B.; Cheng, Z.-R.; Jiao, N. Chin. J. Chem. 2024, 42, 1157.
(g) Zhang, J.-H.; Wang, J.-J.; Cheng, Q. Chin. J. Chem. 2024, 42, 1009.
(h) Xiao, W.; C, J.-Q.; W. J. Chem. Soc. Rev. 2025, 54, 6832.
[4] Nanda B.; Sailu M. S.; Priyaranjan P. M.; Ranjan P. K. P.; Nanda, B. B. Materials Today: Proceedings.2021, 47, 1234.
[5] Anastas P. T.;Warner J. C.Green Chemistry: Theory and Practice, Oxford University Press, New York, 1998.
[6] Breslow, R. Acc. Chem. Res. 1991, 24, 159.
[7] (a) Li, C.-J. Chem. Rev. 1993, 93, 2023.
(b) Lindström, U. M. Chem. Rev. 2002, 102, 2751.
(c) Breslow, R. Acc. Chem. Res. 2004, 37, 471.
(d) Li, C.-J. Chem. Rev. 2005, 105, 3095.
(e) Levin, E.; Ivry, E.; Diesendruck, C. E.; Lemcoff, N.G. Chem. Rev. 2015, 115, 4607.
(f) Sun, K.; Lv, Q.-Y.; Chen, X.-L.; Qu, L.-B.; Yu, B. Green Chem. 2021, 23, 232.
(g) Barata-Vallejo, S.; Yerien, D. E.; Postigo, A. ACS Sustainable Chem. Eng. 2021, 9, 10016.
(h) Russo, C.; Brunelli, F.; Tron, G. C.; Giustiniano, M. J. Org. Chem. 2023, 88, 6284.
(i) Yang, C.-R.; Wang, H.-H.; Xie, P. ChemSusChem. 2025, 18, e202401915.
[8] (a) Li, S.-L.; Zhu, B.; Lee, R.; Qiao, B.-K.; Jiang. Z.-Y. Org. Chem. Front. 2018, 5, 380.
(b) Zhu, X.-J.; Liu, Y.; Liu, C.; Yang, H.-J.; Fu, H. Green Chem. 2020, 22, 4357.
(c) Hosseini-Sarvari, M.; Dehghani, A. New J. Chem. 2020, 44, 16776.
(d) Li, W.-J.; Li, S.; Luo, L.-H.; Ge, Y.-C.; Xu, J.-Q.; Zheng, X.-L.; Yuan, M.-L.; Li, R.- X.; Chen H.; Fu, H.-Y. Green Chem. 2021, 23, 3649.
(e) Zhao, J.-N.; Sun, H.-N.; Lu, Y.; Li, J.-N.; Yu, Z.-Y.; Zhu, H.-F.; Ma, C.-F.; Meng, Q.-W.; Peng, X.-J. Green Chem. 2022, 24, 8503.
[9] Xie P.; Xue C.; Shi S.-S.; Du D.-D. ChemSusChem.2021, 14, 2689.
[10] Bo C.-B.; Bu Q.-Q.; Liu J.-C.; Dai B.; Liu, N. ACS Sustainable Chem. Eng.2022, 10, 1822.
[11] (a) Hirashima, S.-i.; Nobuta, T.; Tada, N.; Miura, T.; Itoh, A. Org. Lett. 2010, 12, 3645.
(b) Nobuta, T.; Fujiya, A.; Hirashima, S.-i.; Tada, N.; Miura, T.; Itoh, A. Tetrahedron Lett. 2012, 53, 5306.
(c) Tripathi, S.; Singh, S. N.; Yadav, L. D. S. RSC Adv. 2016, 6, 14547.
(d) Yunusova, S. N.; Bolotin, D. S.; Vovk, M. A.; Tolstoy, P. M.; Kukushkin, V. Y. Eur. J. Org. Chem. 2020, 2020, 6763.
(e) Kumar, S.; Shah, T. A.; Punniyamurthy, T. Org. Chem. Front. 2021, 8, 4288.
(f) Tu, M.; Chen, B.-J.; Rukhsana, Cui, W.-Y.; Fu, W.-T.; Shen, C.-S.; Shen, Y.-M. New J. Chem. 2022, 46, 23276.
[12] (a) Nishina, Y.; Ohtani, B.; Kikushima, K. Beilstein J. Org. Chem. 2013, 9, 1663.
(b) Talukdar, R. Org. Biomol. Chem. 2020, 18, 8294.
(c) He, X.; Yao, X.-Y.; Cai, S.-F.; Li, H.-R.; He, L.-N. Chem. Commun. 2022, 58, 5845.
[13] Bo C.-B.; Li M.; Chen F.; Liu J.-C.; Dai B.; Liu N. ChemSusChem.2024, 17, e202301015.
[14] (a) Wang A.-Z.; Jiang, H.-F. J. Org. Chem.2010, 75, 2321.
(b) Tang Q.-H.; Wang Y.-Y.; Zhang J.; Qiao R.; Xie X.-P.; Wang Y.; Yang, Y.-H. Appl. Organomet. Chem.2016, 30, 435.
(c) Amaya, T.; Fujimoto, H. Tetrahedron Lett. 2018, 59, 2657.
[15] Xie P.; Xue C.; Luo J.-F.; Shi S.-S.; Du D.-D. Green Chem.2021, 23, 5936.
[16] Zhang Y.-L.; Yue X.-G.; Liang C.-F.; Zhao J.-M.; Yu W.-B.; Zhang P.-F. Tetrahedron Lett.2021, 80, 153321.
[17] (a) Wang, D.-H.; Wang, F.; Chen, P.-H.; Lin, Z.-Y.; Liu, G.-S.Angew. Chem. Int. Ed. 2017, 56, 2054.
(b) Hazra S.; Kaur G.; Handa, S. ACS Sustainable Chem. Eng.2021, 9, 5513.
(c) Shee, M.; Singh, N.D.P. Chem. Soc. Rev. 2022, 51, 2255.
[18] Yue X.-G.; Ouyang Y.-N.; Zhu J.-S.; Yue J.-F.; Peng J.-H.; Li, W.-M. Asian J. Org. Chem.2023, 12, e202300124.
[19] Li, W.-J.; Liu, C.-Y.; Liang, L.-L.; Zhang, J.; Miao, Y.-Q.; Org. Chem. Front. 2024, 11, 5429.
[20] Gu J.-Y.; Yang H.; Deng J.-F.; Jiang D.-B.; Lv K.-Z.; Wang T.; Yao Q.-L.Org. Chem. Front. 2024, 11, 1910.
[21] (a) Song, J. J.; Reeves, J. T.; Gallou, F.; Tan, Z.-L.; Yee, N. K.; Senanayake, C. H. Chem. Soc. Rev. 2007, 36, 1120.
(b) Baraldi, P. G.; Tabrizi, M. A.; Gessi, S.; Borea, P. A. Chem. Rev. 2008, 108, 238.
(c) Archna, Pathania, S.; Chawla, P. A. Bioorg. Chem. 2020, 101, 104026.
(d) Feng, Y.-D.; Zhang, Z.-Y.; Fu, Q.; Yao, Q.-H.; Huang, J.-H.; Shen, H.-B.; Cui, X.-L. Chin. Chem. Lett. 2020, 31, 58.
(e) Yang, H.-Y.; Wang, Y.-F.; Wang, Y.; Zhang, Z.-Y.; Ma, H.-L.; Yamauchi, Y.; Ling, K.-J.; Zhao, Y.; Cai, S.-Z.; An, Z.-F.; Huang, W. Adv. Mater. 2025, 37, e03550.
[22] (a) Matcha, K.; Antonchick, A. P. Angew. Chem. Int. Ed. 2013, 52, 2082.
(b) Garza-Sanchez, R. A.; Tlahuext-Aca, A.; Tavakoli, G.; Glorius, F. ACS Catal. 2017, 7, 4057.
(c) Candish, L.; Freitag, M.; Gensch, T.; Glorius, F. Chem. Sci. 2017, 8, 3618.
(d) Cheng, W.-M.; Shang, R.; Fu, Y. ACS Catal. 2017, 7, 907.
(e) Galloway, J. D.; Mai, D. N.; Baxter, R. D. Org. Lett. 2017, 19, 5772.
[23] (a) Ries, U. J.; Priepke, H. W. M.; Hauel, N. H.; Handschuh, S.; Mihm, G.; Stassen, J. M.; Wienen, W.; Nar, H. Bioorg. Med. Chem. Lett. 2003, 13, 2297.
(b) Liu, R.; Huang, Z.-H.; Murray, M. G.; Guo, X.-Y.; Liu, G. J. Med. Chem. 2011, 54, 5747.
(c) Hussain, S.; Parveen, S.; Hao, X.; Zhang, S.-Z.; Wang, W.; Qin, X.-Y.; Yang, Y.-C.; Chen, X.; Zhu, S.-J.; Zhu, C.-J.; Ma, B. Eur. J. Med. Chem. 2014, 80, 383.
(d) Ke, Q.-M.; Yan, G.-M.; Yu, J.; Wu, X.-M. Org. Biomol. Chem. 2019, 17, 5863.
[24] Gao Y.-H.; Zhao L.-L.; Xiang T.-Y.; Li P.-H.; Wang L. RSC Adv.2020, 10, 10559.
[25] Hong G.-F.; Yuan J.-W.; Fu J.-H.; Pan G.-Y.; Wang Z.-W.; Yang L.-R.; Xiao Y.-M.; Mao P.; Zhang, X.-M. Org. Chem. Front.2019, 6, 1173.
[26] Zhou J.-D.; Ren Q.-L.; Xu N.; Wang C.-D.; Song S.-J.; Chen Z.; Li J.-J. Green Chem.2021, 23, 5753.
[27] Yang Z.-L.; Cao K.; Peng X.-Y.; Lin L.; Fan D.-C.; Li J.-L.; Wang J.-X.; Zhang X.-B.; Jiang H.-Z.; Li J.-H.Chin. J. Chem. 2021, 39, 3347.
[28] Ma C.-H.; Zhao L.; He X.; Jiang Y.-Q.; Yu, B. Org. Chem. Front.2022, 9, 1445.
[29] (a) Jin, J.; MacMillan, D. W. Angew. Chem. Int. Ed. 2015, 54, 1565.
(b) Quattrini, M. C.; Fujii, S.; Yamada, K.; Fukuyama, T.; Ravelli, D.; Fagnoni, M.; Ryu, I. Chem. Commun. 2017, 53, 2335.
(c) Xu, P.; Chen, P.-Y.; Xu, H.-C. Angew. Chem., Int. Ed. 2020, 59, 14275.
(d)Huang, H.; Strater, Z. M.; Lambert, T. H. J. Am. Chem. Soc. 2020, 142, 1698.
(e)Liu, Y.-C.; Shi, B.-Y.; Liu, Z.; Gao, R.-F.; Huang, C.-L.; Alhumade, H.; Wang, S.-C.; Qi, X.-T.; Lei, A.-W. J. Am. Chem. Soc. 2021, 143, 20863.
[30] Yang J.-F.; Liu Y.-F.; Wei L.-L.; Qiao K.-K.; Zhao Y.-Q.; Shi, L. J. Org. Chem.2024, 89, 4249.
[31] Liu A.-D.; Wang Z.-L.; Liu L.; Cheng, L. J. Org. Chem.2021, 86, 16434.
[32] (a) Yi H.; Zhang G.-Y.; Wang H.-M.; Huang Z.-Y.; Wang J.; Singh A. K.; Lei A.-W. Chem. Rev.2017, 117, 9016.
(b) Xie J.; Jin H.-M.; Hashmi, A. S. K. Chem. Soc. Rev.2017, 46, 5193.
(c) Sun, J.-W.; He, J.-Y.; Massaro, L.; Cagan, D. A.; Tsien, J.; Wang, Y.; Attard, F. C.; Smith, J. E.; Lee, J. S.; Kawamata, Y.; Baran, P. S. Nature. 2025, 642, 85.
[33] Xu Y.-W.; Xu X.-Z.; Wu B.; Gan C.-L.; Lin X.-Y.; Wang J.; Ke, F. Asian J. Org. Chem.2020, 9, 1032.
[34] Li X.-H.; Cui W.-W.; Deng Q.-R.; Song X.-Y.; Lv J.; Yang D.-S. Green Chem.2022, 24, 1302.
[35] Zhen J.-S.; Li Y.-H.; Yuan H.; Xu X.-H.; Du X.; Li X.-Q.; Luo, Y. Org. Chem. Front.2023, 10, 404.
[36] Hui X.; Zhang D.; Wu C.-Y.; Ma Y.-F.; Zhou H.-H.; Zhu Y.-B. Green Chem.2023, 25, 2274.
[37] Li M.-F.; Cheng X. Nat Commun.2024, 15, 7540.
[38] (a) Jiang H.; Studer, A. Chem. Soc. Rev.2020, 49, 1790.
(b) Yang H.-F.; Wang Y.-R.; Wang L.-C.; Wu X.-F. EES Catal.2024, 2, 1247.
(c) Ma, B.; Zhao, Z.; Ma, M.; Zhang, R.; Yang, J.-Y. Org. Chem. Front. 2025, 12, 3636., 7681.
(d) Gu, L.-J.; Xu, R.-Y.; Huan, W.-W.; Zhang, Y. Org. Biomol. Chem. 2025, 23, 7681.
[39] Liu J.-K.; Yao H.; Li X.-N.; Wu H.-Y.; Lin A.-J.; Yao H.-Q.; Xu J.-Y.; Xu, S.-T. Org. Chem. Front.2020, 7, 1314.
[40] Lin L.; Yang Z.-L.; Liu J.-C.; Wang J.-X.; Zheng J.-L.; Li J.-L.; Zhang X.-B.; Liu X.-W.; Jiang H.-Z.; Li J.-H. Green Chem.2021, 23, 5467.
[41] Sun B.; Tang X.-L.; Zhuang X.-H.; Ling L.; Huang P.-Y.; Wang J.-Y.; Jin, C. Adv. Synth. Catal.2023, 365, 1020.
[42] Wang Z.-K.; Wang L.-X.; Lin H.; Qiu B.; Ma Y.-C.; Xiao J.; An X.-D. Green Chem.2025, 27, 4565.
[43] Renzi P.; Rusconi M.; Ghigo G.; Deagostinoa A.Adv. Synth. Catal. 2023, 365, 4623.
[44] Zhu B.-F.; Ponnam D.; Li M.-Z.; Li G.-K.; Fan R.-F.; Chen J.-C.; Fan, B.-M. J. Org. Chem.2025, 90, 7738.
[45] Yan K.-C.; He H.; Li J.-L.; Luo Y.; Lai R.-Z.; Guo L.; Wu, Y. Chin. Chem. Lett.2021, 32, 3984.
[46] Xu P.; Huang P.-Y.; Jiang Y.; Lv C.; Li P.-X.; Wang J.-Y.; Sun B.; Jin C. Green Chem.2023, 25, 8741.
[47] (a) Duddeck H.; Bradenahl R.; Stefaniak L.; Jazwinski J.;Kamienski, B. Magn. Reson. Chem.2001, 39, 709.
(b) Liu, J.; Xu, S.-J.; Huang, C.; Shen, J.-T.; Yu, S.; Yu, Y.-Z.; Sun, Q.-Y.; Dai, Q.-Y. Bioorg. Med. Chem. Lett. 2022, 73, 128913.
[48] Hasan C.; Hunter R. F.J. Chem. Soc. 1935, 1762.
[49] Ji H.-T.; Wang K.-L.; Ouyang W.-T.; Luo Q.-X.; Li H.-X.; He W.-M. Green Chem.2023, 25, 7983.
[50] (a) Olack G.; Morrison, H. J. Org. Chem.1991, 56, 4969.
(b) Guanti G.; Banfi L.; Powles K.; Rasparini M.; Scolastico C.; Fossati N. Tetrahedron: Asymmetry.2001, 12, 271.
(c) Christoffers, J.; Werner, T.; Frey, W.; Baro, A. Chem. Eur. J. 2004, 10, 1042.
[51] (a) Liang Y.-F.; Jiao, N. Angew. Chem. Int. Ed.2014, 53, 548.
(b) Chaudhari, M. B.; Sutar, Y.; Malpathak, S.; Hazra, A.; Gnanaprakasam, B. Org. Lett. 2017, 19, 3628.
(c) Wang Y.-T.; Lu R.; Yao J.; Li, H.-R. Angew. Chem. Int. Ed. 2021, 60,6631.
(d) He, Y.-J.; Yin, H.; Wang, Y.-F.; Chu, M.-M.; Li, Y.-M.RSC Adv. 2023, 13, 7843.
[52] Wang Y.; Wang Z.-J.; Luo H.; Wang G.-H.; Shi, Z.-D. Ma Y.-F.; Wu J.-L.; Li D.-J.; Yang, J.-H. Org. Chem. Front.2024, 11, 5524.
[53] (a) Sauer, G. S.; Lin, S. ACS Catal. 2018, 8, 5175.
(b) Xiong, P.; Long, H.; Song, J.-S.; Wang, Y.-H.; Li, J.-F.; Xu, H.-C. J. Am. Chem. Soc. 2018, 140, 16387.
(c) Zhang, W.; Lin, S. J. Am. Chem. Soc. 2020, 142, 20661.
(d) Song, L.; Fu, N.-K.; Ernst, B. G.; Lee, W.-H.; Frederick, M. O.; DiStasio, R. A.; Lin, S. Nat. Chem. 2020, 12, 747.
(e) Siu, J. C.; Fu, N.-K.; Lin, S. Acc. Chem. Res. 2020, 53, 547.
(f) Wang, Y.-L.; Dana, S.; Long, H.; Xu, Y.; Li, Y.-J.; Kaplaneris, N.; Ackermann, L. Chem. Rev. 2023, 123, 11269.
[54] Li M.-F.; Pu T.-F.; Cheng X.Synthesis. 2025, 57, 2063.