光、电化学驱动芳基自由基的形成和转化研究

doi:10.12461/PKU.DXHX202405124

大学化学 >> 2025, Vol. 40 >> Issue (2): 201-209.doi: 10.12461/PKU.DXHX202405124

所属专题：自由基化学

光、电化学驱动芳基自由基的形成和转化研究

成秀亮, 程诗砚, 龚磊

厦门大学化学化工学院, 福建厦门 361005

收稿日期:2024-05-17 录用日期:2024-08-13 发布日期:2025-02-22
通讯作者: 龚磊 E-mail:gongl@xmu.edu.cn
基金资助:
国家自然科学基金(22371237,22071209)

Research on Photochemical and Electrochemical Generation of Aryl Radicals and Their Subsequent Transformations

Xiuliang Cheng, Shiyan Cheng, Lei Gong

College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, China

Received:2024-05-17 Accepted:2024-08-13 Published:2025-02-22
Contact: Lei Gong E-mail:gongl@xmu.edu.cn

摘要/Abstract

摘要： 芳基自由基是许多化学反应的重要中间体，具有独特的电子结构和极高的反应活性，其有效生成和定向转化很具挑战。本文介绍了近年来化学研究者们利用快速发展的光、电化学手段，有效克服了这一难题，用于C―H芳基化等诸多合成反应。这些新颖的底物激活模式和后续转化调控策略，丰富了自由基化学在本科教学层面的内容，也有助于学生深化对自由基反应机制的理解。

关键词: 芳基自由基, 光电催化, 单电子转移

Abstract: Aryl radicals, pivotal intermediates in myriad chemical reactions due to their distinct electronic structure and remarkable reactivity, present formidable challenges in terms of efficient generation and directed transformation. This paper highlights recent advancements where chemists have effectively tackled this challenge by harnessing rapidly evolving photochemical and electrochemical techniques, enabling their use in diverse C―H arylation processes among other syntheses. The innovative substrate activation methods and subsequent reaction control strategies not only enrich the undergraduate curriculum in radical chemistry but also deepen students’ comprehension of radical reaction mechanisms.

Key words: Aryl radical, Photoelectrocatalysis, Single electron transfer

成秀亮, 程诗砚, 龚磊. 光、电化学驱动芳基自由基的形成和转化研究[J]. 大学化学, 2025, 40(2): 201-209.

Xiuliang Cheng, Shiyan Cheng, Lei Gong. Research on Photochemical and Electrochemical Generation of Aryl Radicals and Their Subsequent Transformations[J]. University Chemistry, 2025, 40(2): 201-209.

链接本文: https://www.dxhx.pku.edu.cn/CN/10.12461/PKU.DXHX202405124

https://www.dxhx.pku.edu.cn/CN/Y2025/V40/I2/201

参考文献

[1] Grieve, W. S. M.; Hey, D. H. J. Am. Chem. Soc. 1934, 1966.
[2] Grieve, W. S. M.; Hey, D. H. J. Am. Chem. Soc. 1934, 1797.
[3] Meerwein, H.; Buchner, E.; van Emsterk, K. J. Prakt. Chem. 1939, 152, 237.
[4] Kvasovs, N.; Gevorgyan, V. Chem. Soc. Rev. 2021, 50, 2244.
[5] Studer, A.; Amrein, S. Synthesis 2002, 2002, 835.
[6] Schiesser, C. H.; Sutej, K. Tetrahedron let. 1992, 33, 5137.
[7] Diesendorf, N.; Heinrich, M. R. Synthesis 2022, 54, 1951.
[8] Yanagisawa, S.; Ueda, K.; Taniguchi, T.; Itami, K. Org. Lett. 2008, 10, 4673.
[9] Clark, K. F.; Tyerman, S.; Evans, L.; Robertson, C. M.; Nelson, D. J.; Kennedy, A. R.; Murphy, J. A. J. Am. Chem. Soc. 2023, 145, 20849.
[10] Bhakuni, B. S.; Kumar, A.; Balkrishna, S. J.; Sheikh, J. A.; Konar, S.; Kumar, S. Org. Lett. 2012, 14, 2838.
[11] Lan, J.; Chen, R.; Duo, F.; Hu, M.; Lu, X. Molecules 2022, 27, 5364.
[12] 梁福顺. 辽宁大学学报(自然科学版), 2017, 44, 138.
[13] Wang, L.; Shi, M.; Chen, X.; Su, N.; Luo, W.; Zhang, X. Angew. Chem. Int. Ed. 2019, 62, e202314312.
[14] Patra, T.; Mukherjee, S.; Ma, J.; Strieth‐Kalthoff, F.; Glorius, F. Angew. Chem. Int. Ed. 2019, 58, 10514.
[15] Targos, K.; Williams, O. P.; Wickens, Z. K. J. Am. Chem. Soc. 2021, 143, 4125.
[16] Cai, Y.; Ritter, T. Angew. Chem. Int. Ed. 2022, 61, e202209882.
[17] Xu, J.; Cao, J.; Wu, X.; Wang, H.; Yang, X.; Tang, X.; Toh, R. W.; Zhou, R.; Yeow, E. K. L.; Wu, J. J. Am. Chem. Soc. 2021, 143, 13266.
[18] Crisenza, G. E.; Mazzarella, D.; Melchiorre, P. J. Am. Chem. Soc. 2020, 142, 5461.
[19] Kvasovs, N.; Gevorgyan, V. Chem. Soc. Rev. 2021, 50, 2244.
[20] Cheng, X.; He, Y.; Song, S.; Lin, Y. M.; Gong, L. Chem. Commun. 2023, 59, 9513.
[21] 蒋洋叶. 光/电协同生成甲氧自由基和苯自由基的串联反应研究[博士学位论文]. 北京: 北京工业大学, 2021.
[22] Malviya, B. K.; Singh, K.; Jaiswal, P. K.; Karnatak, M.; Verma, V. P.; Badsara, S. S.; Sharma, S. New J. Chem. 2021, 45, 6367.
[23] Kong, X.; Chen, Y.; Chen, X.; Ma, C.; Chen, M.; Wang, W.; Xu, Y. Q.; Ni, S. F.; Cao, Z. Y. Nat. Commun. 2023, 141, 6933.
[24] 井强山, 王帅. 许昌专师学报. 2000, 19 (2), 31.

光、电化学驱动芳基自由基的形成和转化研究

Research on Photochemical and Electrochemical Generation of Aryl Radicals and Their Subsequent Transformations

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 4

Metrics

推荐阅读 0

[1]	曹中艳, 金胜男, 王玉霞, 陈依漪, 孔宪强, 徐元清. 酚类衍生物作为芳基自由基前体参与的高选择性反应进展[J]. 大学化学, 2025, 40(4): 245 -252 .
[2]	刘瑞涛, 潘本鸿, 潘能慧, 徐亮, 栗振华. 新实验开发：三氧化钨光阳极的制备、表征以及在苯甲醚卤化中的应用[J]. 大学化学, 2025, 40(1): 309 -317 .
[3]	吴宁然, 田恩麟, 赵创源, 沈永雯, 惠新平, 景欢旺. 半导体纳米复合材料的制备及其光电催化CO₂还原[J]. 大学化学, 2020, 35(4): 66 -71 .
[4]	许家喜. 芳基离子及芳基自由基与环己二烯离子及环己二烯自由基的区别[J]. 大学化学, 2013, 28(3): 77 -81 .