铁催化电化学转化研究进展

doi:10.6023/cjoc202602024

摘要/Abstract

近年来, 有机电化学因其具有条件温和、绿色高效的优点, 得到了快速发展. 与此同时, 铁催化剂因其成本低廉、储量丰富且价态、自旋态多变可调, 有效弥补了传统贵金属催化剂价格高、可持续性差的不足. 铁催化电化学转化的发展, 为现代有机合成化学提供了绿色、高效且可持续的合成工具, 目前已广泛应用于氧化、还原及偶联等各类反应体系中. 综述了该领域的最新研究进展, 总结了铁催化氧化反应、还原反应以及氧化还原配对反应三类反应体系, 阐述了相应的催化机制和代表性反应, 并对铁催化的电化学转化进行了展望.

关键词: 铁催化, 有机电化学, 氧化还原反应

In recent years, organic electrochemistry has developed rapidly due to its mild conditions, environmental friendliness and high efficiency. Meanwhile, iron catalysts have effectively compensated for the high cost and poor sustainability of traditional noble-metal catalysts due to their low price, abundant reserves, and tunable of their valence and spin states. The development of iron-catalyzed electrochemical transformations has provided green, efficient, and sustainable synthetic tools for modern organic synthesis. Presently, such strategies have been widely applied in various reaction systems including oxidation, reduction, and coupling reactions. This review summarizes the latest advances in this field, focusing on three categories of iron-catalyzed electrochemical reactions: oxidative, reductive, and redox-paired transformations. The corresponding catalytic mechanisms and representative reactions are discussed, and an outlook on iron-catalyzed electrochemical transformations is also provided.

Key words: iron catalysis, organic electrochemistry, redox reaction

引用此文

杨林静, 赵志伟, 石安仔, 杨国庆, 仇友爱. 铁催化电化学转化研究进展[J]. 有机化学, 2026, 46(7): 2511-2528.

Linjing Yang, Zhiwei Zhao, Anzai Shi, Guoqing Yang, Youai Qiu. Advances in Iron-Catalyzed Electrochemical Transformations[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2511-2528.

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图/表 16

图1. 铁催化电化学转化

Figure 1. Iron-catalyzed electrochemical transformations

图2. 铁在阳极/阴极的不同反应路径

Figure 2. Distinct reaction pathways of iron at the anode and cathode

图式1. 未活化烯烃与亚甲基化合物的电化学环丙烷化反应

Scheme 1. Electrochemical cyclopropanation of unactivated alkenes with methylene compounds

图式2. 电化学C—H/N—H官能团化合成(氮杂)吲哚

Scheme 2. Electrochemical C—H/N—H functionalization for the synthesis of highly functionalized (aza) indoles

图式3. 铁-氧(Fe-oxo)物种参与的以水为氧源电化学C—H键氧化与醇脱氢反应

Scheme 3. Electrochemical C—H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source

图式4. 环状N-芳基胺的电化学去饱和β-酰化

Scheme 4. Electrochemical desaturative β-acylation of cyclic N-aryl amines

图式5. 光电化学驱动的铁催化烷烃C(sp3)—H硼化反应

Scheme 5. Photoelectrochemically driven iron-catalysed C(sp3)—H borylation of alkanes

图式6. 铁催化聚合物解聚反应

Scheme 6. Iron-catalyzed polymer depolymerization reaction

图式7. 铁催化光电化学硅基环丁醇α-官能化反应

Scheme 7. Iron-catalyzed electrophotochemical α-functionalization of a silylcyclobutanol

图式8. 光电化学铁催化C—H键氟代烷基化反应

Scheme 8. Photoelectrochemical iron(III) catalysized C—H fluoroalkylations

图式9. 电化学低价铁催化构建炔基-锗化合物

Scheme 9. Alkynyl-germanium architectures through electrochemical low-valent iron-catalyzed conjunctive coupling

图式10. 铁电催化脱氧Giese反应

Scheme 10. Fe-electrocatalytic deoxygenative Giese reaction

图式11. 低价态铁电催化醛类化合物制备活性卡宾

Scheme 11. Carbene reactivity directly from aldehydes via low-valent iron electrocatalysis

图式12. 配对氧化与还原催化: 突破电化学C(sp3)—H烯基化的势垒

Scheme 12. Paired oxidative and reductive catalysis: breaking the potential barrier of electrochemical C(sp3)—H alkenylation

图式13. 电化学双金属催化芳基卤化物的二氟甲基化反应

Scheme 13. Dual metal electrocatalysis for difluoromethylation of aryl halides

图式14. 光电协同催化双金属参与配对电解醇的芳基化反应

Scheme 14. Photoelectrocatalytic bimetallic paired electrolysis for arylations of alcohols

参考文献 76

[1]	Zhu, Z. L.; Li, P. F.; Qiu, Y. A. Chin. J. Org. Chem. 2024, 44, 871 (in Chinese). doi: 10.6023/cjoc202310033
	(朱子乐, 李鹏飞, 仇友爱, 有机化学, 2024, 44, 871.) doi: 10.6023/cjoc202310033
[2]	Zhang, Y.; Ma, C.; Cai, Z.; Struwe, J.; Chen, S.; Xu, J.; Li, S.; Zeng, W.; Ackermann, L. Green Chem. 2022. 24, 3697. doi: 10.1039/d2gc00684g pmid: 35694222
[3]	Shi, A.; Liu, Y.; Zhang, R.; Zhu, Z.; Qiu, Y. eScience 2024, 4, 100255. doi: 10.1016/j.esci.2024.100255
[4]	Yang, G.; Jia, J.; Deng, Y.; Qiu, Y. Natl. Sci. Rev. 2026, 13, nwag047.
[5]	Kou, G.; Li, P.; Yang, G.; Qiu, Y. CCS Chem. 2025, 7, 3005. doi: 10.31635/ccschem.024.202404697
[6]	Ma, D.; Qiu, Y. Chin. Chem. Lett. 2025, 111892.
[7]	Zeng, W.; Qiu, Y. Chin. Chem. Lett. 2025, 111679.
[8]	Pan, Y.; Meng, X.; Wang, Y.; He, M. Chin. J. Org. Chem. 2023, 43, 1416 (in Chinese). doi: 10.6023/cjoc202208004
	(潘永周, 蒙秀金, 王迎春, 何慕雪, 有机化学, 2023, 43, 1416.) doi: 10.6023/cjoc202208004
[9]	Yang, G.; Wang, Y. W.; Qiu, Y. A. Chin. J. Org. Chem. 2021, 41, 3935 (in Chinese). doi: 10.6023/cjoc202105054
	(杨光, 王衍伟, 仇友爱, 有机化学, 2021, 41, 3935.)
[10]	Wang, C. R.; Zhang, W. Y.; Yu, C.; Li, Y.; Li, J. H. Chin. J. Chem. 2025, 43, 3676. doi: 10.1002/cjoc.v43.24
[11]	Lu, J.; Wang, Y.; McCallum, T.; Fu, N. iScience 2020, 23, 101796. doi: 10.1016/j.isci.2020.101796
[12]	Kim, J. H.; Jang, J. W.; Kang, H. J.; Magesh, G.; Kim, J. Y.; Kim, J. H.; Lee, J. S. J. Catal. 2014, 317, 126. doi: 10.1016/j.jcat.2014.06.015
[13]	Zhou, Y.; Xu, W.; Wei, Z.; Tian, D.; Zhu, B.; Qiao, S.; Song, L. Angew. Chem., Int. Ed. 2025, 64, e202412901. doi: 10.1002/anie.v64.1
[14]	Xu, F.; Li, Y. J.; Huang, C.; Xu, H. C. ACS Catal. 2018, 8, 3820. doi: 10.1021/acscatal.8b00373
[15]	Chen, G.; He, P.; Liu, C.; Mo, X. F.; Wei, J. J.; Chen, Z. W.; Yi, X. Y. Nat. Catal. 2023, 6, 949. doi: 10.1038/s41929-023-01025-z
[16]	Wei, W. J.; Zhan, L.; Gao, L.; Huang, G. B.; Ma, X. L. Chin. J. Org. Chem. 2023, 43, 17 (in Chinese). doi: 10.6023/cjoc202205018
	(魏琬絜, 詹磊, 高雷, 黄国保, 马献力, 有机化学, 2023, 43, 17.) doi: 10.6023/cjoc202205018
[17]	Ye, Z. H.; Liu, H. Q.; Zhang, F. Z. Chin. J. Org. Chem. 2024, 44, 840 (in Chinese).
	(叶增辉, 刘华清, 张逢质, 有机化学, 2024, 44, 840.) doi: 10.6023/cjoc202310034
[18]	Han, X.; He, C. Chin. J. Chem. 2024, 42, 3414. doi: 10.1002/cjoc.v42.24
[19]	Zhao, Q. Q.; Gu, M.; Chen, J. R. Chin. J. Chem. 2024, 42, 2412. doi: 10.1002/cjoc.v42.19
[20]	Xie, P.; Tang, H.; Shi, A.; Chen, S.; Qiu, Y. eScience 2026, 100553.
[21]	Hourtoule, M.; Skumial, P.; Trienes, S.; Gülen, H. C.; Zhang, J.; Ackermann, L. Angew. Chem., Int. Ed. 2026, 65, e19237. doi: 10.1002/anie.v65.7
[22]	Wadsworth, B. L.; Beiler, A. M.; Khusnutdinova, D.; Jacob, S. I.; Moore, G. F. ACS Catal. 2016, 6, 8048. doi: 10.1021/acscatal.6b02194
[23]	Ibrahim, M. Y.; Cumming, G. R.; Gonzalez de Vega, R.; Garcia-Losada, P.; de Frutos, O.; Kappe, C. O.; Cantillo, D. J. Am. Chem. Soc. 2023, 145, 17023. doi: 10.1021/jacs.3c07313
[24]	Fu, N.; Sauer, G. S.; Saha, A.; Loo, A.; Lin, S. Science 2017, 357, 575. doi: 10.1126/science.aan6206
[25]	Hu, X.; Zeng, Y.; Ma, J.; Diao, H.; Chen, F. X.; Chen, M.; Zhang, S.; Jin, C.; Ni, S.; Ruan, Z. Chin. Chem. Lett. 2025, 111928.
[26]	Shaik, S. Nat. Chem. 2010, 2, 347. doi: 10.1038/nchem.638
[27]	Shang, R.; Ilies, L.; Nakamura, E. J. Am. Chem. Soc. 2015, 137, 7660. doi: 10.1021/jacs.5b04818 pmid: 26061014
[28]	Shang, R.; Ilies, L.; Nakamura, E. J. Am. Chem. Soc. 2016, 138, 10132. doi: 10.1021/jacs.6b06908 pmid: 27487172
[29]	Doba, T.; Matsubara, T.; Ilies, L.; Shang, R.; Nakamura, E. Nat. Cat. 2019, 2, 400.
[30]	Norinder, J.; Matsumoto, A.; Yoshikai, N.; Nakamura, E. J. Am. Chem. Soc. 2008, 130, 5858. doi: 10.1021/ja800818b pmid: 18410099
[31]	Yoshikai, N.; Matsumoto, A.; Norinder, J.; Nakamura, E. Angew. Chem., Int. Ed. 2009, 48, 2925. doi: 10.1002/anie.v48:16
[32]	Yoshikai, N.; Mieczkowski, A.; Matsumoto, A.; Ilies, L.; Nakamura, E. J. Am. Chem. Soc. 2010, 132, 5568. doi: 10.1021/ja100651t pmid: 20361736
[33]	Mazzacano, T. J.; Mankad, N. P. J. Am. Chem. Soc. 2013, 135, 17258. doi: 10.1021/ja408861p pmid: 24074248
[34]	Mo, J.; Müller, T.; Oliveira, J. C.; Demeshko, S.; Meyer, F.; Ackermann, L. Angew. Chem.,Int. Ed. 2019, 58, 12874. doi: 10.1002/anie.v58.37
[35]	Mo, J.; Müller, T.; Oliveira, J. C. A.; Ackermann, L. Angew. Chem., Int. Ed. 2018, 57, 7719. doi: 10.1002/anie.v57.26
[36]	Zhu, C.; Stangier, M.; Oliveira, J. C. A.; Massignan, L.; Ackermann, L. Chem.-Eur. J. 2019, 25, 16382. doi: 10.1002/chem.v25.71
[37]	Green, S. A.; Vásquez-Céspedes, S.; Shenvi, R. A. J. Am. Chem. Soc. 2018, 140, 11317. doi: 10.1021/jacs.8b05868
[38]	Mako, T. L.; Byers, J. A. Inorg. Chem. Front. 2016, 3, 766. doi: 10.1039/C5QI00295H
[39]	Fürstner, A.; Leitner, A.; Méndez, M.; Krause, H. J. Am. Chem. Soc. 2002, 124, 13856. pmid: 12431116
[40]	Tong, X.; Yang, Z. P.; Del Angel Aguilar, C. E.; Fu, G. C. Angew. Chem., Int. Ed. 2023, 62, e202306663. doi: 10.1002/anie.v62.34
[41]	Bhugun, I.; Lexa, D.; Saveant, J. M. J. Am. Chem. Soc. 1994, 116, 5015. doi: 10.1021/ja00090a068
[42]	Jin, M.; Adak, L.; Nakamura, M. J. Am. Chem. Soc. 2015, 137, 7128. doi: 10.1021/jacs.5b02277
[43]	Kessler, S. N.; Bäckvall, J.-E. Angew. Chem., Int. Ed. 2016, 55, 3734. doi: 10.1002/anie.v55.11
[44]	Xie, Y. Z.; Deng, S. Y.; Mo, S. M.; Wang, M. R.; Wang, G. A.; Tang, H. T.; Pan, Y. M. Chin. J. Chem. 2026, 44, 501. doi: 10.1002/cjoc.v44.4
[45]	Scheiper, B.; Bonnekessel, M.; Krause, H.; Fürstner, A. J. Org. Chem. 2004, 69, 3943. pmid: 15153029
[46]	Liu, M.; Wang, Y.; Gao, C.; Jia, J.; Zhu, Z.; Qiu, Y. Angew. Chem., Int. Ed. 2025, 64, e202425634. doi: 10.1002/anie.v64.9
[47]	Hou, Z. W.; Mao, Z. Y.; Zhao, H. B.; Melcamu, Y. Y.; Lu, X.; Song, J.; Xu, H. C. Angew. Chem., Int. Ed. 2016, 55, 9168. doi: 10.1002/anie.v55.32
[48]	He, J.-Y.; Qian, W. F.; Wang, Y. Z.; Yao, C.; Wang, N.; Liu, H.; Zhong, B.; Zhu, C.; Xu, H. Green Chem. 2022, 24, 2483. doi: 10.1039/D1GC04479F
[49]	Das, A.; Nutting, J. E.; Stahl, S. S. Chem. Sci. 2019, 10, 7542. doi: 10.1039/C9SC02609F
[50]	Feng, T.; Wang, S.; Liu, Y.; Liu, S.; Qiu, Y. Angew. Chem., Int. Ed. 2022, 134, e202115178. doi: 10.1002/ange.v134.6
[51]	Yang, J.; Muhammad, S.; Yi, H.; Zeng, L. SynOpen 2025, 9, 203. doi: 10.1055/a-2709-9625
[52]	Cao, Y.; Huang, C.; Lu, Q. Nat. Synth. 2024, 3, 537. doi: 10.1038/s44160-023-00480-7
[53]	Hourtoule, M.; Trienes, S.; Ackermann, L. Angew. Chem., Int. Ed. 2024, 63, e202412689. doi: 10.1002/anie.v63.48
[54]	Guo, J. J.; Hu, A.; Chen, Y.; Sun, J.; Tang, H.; Zuo, Z. Angew. Chem., Int. Ed. 2016, 55, 15319. doi: 10.1002/anie.v55.49
[55]	An, Q.; Wang, Z. Y.; Chen, Y. G.; Wang, X.; Zhang, K.; Pan, H.; Liu, W.; Zuo, Z. J. Am. Chem. Soc. 2020, 142, 6216. doi: 10.1021/jacs.0c00212
[56]	Zhou, P.; Ding, L.; Liu, Y.; Song, H.; Wang, Q. Org. Lett. 2024, 26, 7094. doi: 10.1021/acs.orglett.4c02279 pmid: 39150853
[57]	Motornov, V.; Trienes, S.; Resta, S.; Oliveira, J. C.; Lin, Z.; Liu, Z.; Ackermann, L. Angew. Chem., Int. Ed. 2025, 64, e202504143. doi: 10.1002/anie.v64.25
[58]	Ohmura, T.; Torigoe, T.; Suginome, M. Organometallics 2013, 32, 6170. doi: 10.1021/om400900z
[59]	Ohmura, T.; Torigoe, T.; Suginome, M. J. Am. Chem. Soc. 2012, 134, 17416. doi: 10.1021/ja307956w
[60]	Wang, Y.; Dana, S.; Long, H.; Xu, Y.; Li, Y.; Kaplaneris, N.; Ackermann, L. Chem. Rev. 2023, 123, 11269. doi: 10.1021/acs.chemrev.3c00158
[61]	Sauermann, N.; Meyer, T. H.; Qiu, Y.; Ackermann, L. ACS Catal. 2018, 8, 7086. doi: 10.1021/acscatal.8b01682
[62]	Liang, X. A.; Liu, D.; Sun, H.; Jiang, C.; Chen, H.; Niu, L.; Mahato, K.; Abdelilah, T.; Zhang, H.; Lei, A. Adv. Synth. Catal. 2020, 362, 1138. doi: 10.1002/adsc.v362.5
[63]	Huang, B.; Sun, Z.; Sun, G. eScience 2022, 2, 243. doi: 10.1016/j.esci.2022.04.006
[64]	Chen, H.; Rueping, M. Angew. Chem., Int. Ed. 2025, 64, e202516109. doi: 10.1002/anie.v64.46
[65]	Zou, L.; Xiang, S.; Zhang, Y.; Yi, X.; Zheng, X.; Zhang, J. Q.; Lu, Q. J. Am. Chem. Soc. 2025, 147, 45566. doi: 10.1021/jacs.5c16668
[66]	Yu, L.; Li, S.; Ogawa, H.; Ma, Y.; Chen, Q.; Yamazaki, K.; Nakamura, H. Nat. Commun. 2025, 16, 8379. doi: 10.1038/s41467-025-63515-x
[67]	Zheng, Y. T.; Wu, Y. X.; Yang, N.; Ma, Z. H.; Wang, G.; Lang, K.; Xu, H. C. J. Am. Chem. Soc. 2025, 147, 43254. doi: 10.1021/jacs.5c17027
[68]	Zhang, L.; Ritter, T. J. Am. Chem. Soc. 2022, 144, 2399. doi: 10.1021/jacs.1c10783 pmid: 35084173
[69]	Li, N.; Sitdikov, R.; Kale, A. P.; Steverlynck, J.; Li, B.; Rueping, M. J. Org. Chem. 2024, 20, 2500.
[70]	Liu, C.; Zhang, R.; Liu, Y.; Zhang, Y. Chin. J. Chem. 2025, 43, 3302. doi: 10.1002/cjoc.v43.23
[71]	Zou, L.; Wang, X.; Xiang, S.; Zheng, W.; Lu, Q. Angew. Chem., Int. Ed. 2023, 62, e202301026. doi: 10.1002/anie.v62.24
[72]	Wan, Q.; Liu, R. X.; Zhang, Z.; Wu, X. D.; Hou, Z. W.; Wang, L. Chin. J. Chem. 2024, 42, 1913. doi: 10.1002/cjoc.v42.16
[73]	Zhou, N.; Chai, M.; Fu, N. Nat. Commun. 2025, 16, 10734. doi: 10.1038/s41467-025-65763-3
[74]	Guillemard, L.; Kaplaneris, N.; Ackermann, L.; Johansson, M. Nat. Rev. Chem. 2021, 5, 522. doi: 10.1038/s41570-021-00300-6 pmid: 37117588
[75]	Liu, Z. R.; Zhu, X. Y.; Guo, J. F.; Ma, C.; Zuo, Z.; Mei, T. S. Sci. Bull. 2024, 69, 1866. doi: 10.1016/j.scib.2024.04.031
[76]	Zou, L.; Sun, R.; Tao, Y.; Wang, X.; Zheng, X.; Lu, Q. Nat. Commun. 2024, 15, 5245. doi: 10.1038/s41467-024-49557-7