Recent Advances in Electrophotochemical Transition Metal Catalysis

doi:10.6023/cjoc202409038

Abstract

Electrophotochemical transition metal catalysis integrates the characteristics of photochemistry, electrochemistry, and transition metal catalysis, providing an elegant approach for selective generation and transformation of highly reactive radical species in synthetic chemistry. Photoredox catalysts can gain or lose electrons on the electrode surface to form the corresponding photosensitizers, avoiding the use of stoichiometric redox reagents in traditional photochemical reactions. The metal catalysts in the system can both act as electrocatalysts to transfer electrons between electrodes and substrates, and interact with substrates to control the reaction pathways. This novel catalytic strategy harnesses both light and electrical energy as the driving force for the reaction, substantially reducing the electrode potential and enabling electron transfer activation processes that are commonly challenging to achieve under otherwise mild conditions. The research progress of this new field of research in the past few years is summarized, and the prospects of further developments are also discussed.

Key words: electrophotocatalysis, transition metal, redox, radical

Cite this article

Yan Yao, Niankai Fu. Recent Advances in Electrophotochemical Transition Metal Catalysis[J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 1819-1837.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 24

Scheme 1. Early examples of electrophotocatalysis in oxidation reactions

Figure 1. Electrochemical oxidation enabled regeneration of photoredox catalyst

Figure 2. Electrochemical oxidation generated photoredox catalyst

Figure 3. Electrochemical reduction generated photoredox catalyst

Figure 4. Electrophotocatalytic C—H trifluoromethylation

Figure 5. Electrophotocatalytic cross-dehydrogenative coupling of benzothiazoles with aliphatic C—H bonds

Figure 6. Electrophotocatalytic hydroxyalkylation of heteroaromatics with aldehydes

Figure 7. Electrophotochemical Ce-catalyzed decarboxylative alkylation of heteroarenes

Figure 8. Electrophotochemical Fe-catalyzed decarboxylative alkylation of heteroarenes

Figure 9. Electrophotochemical Ce-catalyzed Minisci alkylation of N-heteroarenes with alkanes

Figure 10. Electrophotochemical Ce-catalyzed ring-opening functionalization of cycloalkanols

Figure 11. Electrophotochemical Fe-catalyzed C(sp3)-H borylation of alkanes

Figure 12. Electrophotocatalytic azidation of C(sp3)—H bonds

Figure 13. Ce/Mn dual electrophotocatalytic decarboxylative azidation of aliphatic acids

Figure 14. Ce/Cu dual electrophotocatalytic asymmetric decarboxylative cyanation

Figure 15. Electrophotochemical Cu-catalyzed asymmetric cyanation of benzylic C—H bonds

Figure 16. Electrophotochemical Cu-catalyzed asymmetric heteroarylcyanation of aryl alkenes

Figure 17. Ce/Ni dual electrophotocatalytic decarboxylative arylation of aliphatic acids

Figure 18. Ce/Ni dual electrophotocatalytic decarboxylative alkenylation of aliphatic acids

Figure 19. Fe/Ni dual electrophotocatalytic C(sp3)−H alkenylation

Figure 20. Fe/Ni dual electrophotocatalytic alkylarylation of alkenes with alkanes

Figure 21. Fe/Ni dual electrophotocatalytic carboacylation of alkenes with alkanes

Figure 22. Ce/Ni dual electrophotocatalytic deconstructive arylation of alcohols

Figure 23. Electrophotocatalytic asymmetric dehydrogenative [2＋2] cycloaddition

References 97

[1]	Trost, B. M. Science 1991, 254, 1471.
[2]	Sheldon, R. A. ACS Sustainable Chem. Eng. 2017, 6, 32.
[3]	(a) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322.
	(b) Shaw, M. H.; Twilton, J.; MacMillan, D. W. C. J. Org. Chem. 2016, 81, 6898.
	(c) Twilton, J.; Le, C.; Zhang, P.; Shaw, M. H.; Evans, R. W.; MacMillan, D. W. C. Nat. Rev. Chem. 2017, 1, 0052.
	(d) Chan, A. Y.; Perry, I. B.; Bissonnette, N. B.; Buksh, B. F.; Edwards, G. A.; Frye, L. I.; Garry, O. L.; Lavagnino, M. N.; Li, B. X.; Liang, Y.; Mao, E.; Millet, A.; Oakley, J. V.; Reed, N. L.; Sakai, H. A.; Seath, C. P.; MacMillan, D. W. C. Chem. Rev. 2022, 122, 1485.
	(e) Romero, N. A.; Nicewicz, D. A. Chem. Rev. 2016, 116, 10075.
	(f) Narayanam, J. M. R.; Stephenson, C. R. J. Chem. Soc. Rev. 2011, 40, 102.
[4]	(a) Yoshida, J.-I.; Kataoka, K.; Horcajada, R.; Nagaki, A. Chem. Rev. 2008, 108, 2265.
	(b) Francke, R.; Little, R. D. Chem. Soc. Rev. 2014, 43, 2492.
	(c) Yan, M.; Kawamata, Y.; Baran, P. S. Chem. Rev. 2017, 117, 13230.
	(d) Wiebe, A.; Gieshoff, T.; Mohle, S.; Rodrigo, E.; Zirbes, M.; Waldvogel, S. R. Angew. Chem. Int. Ed. 2018, 57, 5594.
[5]	(a) Siu, J. C.; Fu, N.; Lin, S. Acc. Chem. Res. 2020, 53, 547.
	(b) Novaes, L. F. T.; Liu, J.; Shen, Y.; Lu, L.; Meinhardt, J. M.; Lin, S. Chem. Soc. Rev. 2021, 50, 7941.
	(c) Yuan, Y.; Yang, J.; Lei, A. Chem. Soc. Rev. 2021, 50, 10058.
	(d) Xiong, P.; Xu, H.-C. Acc. Chem. Res. 2019, 52, 3339.
	(e) Jiao, K.-J.; Xing, Y.-K.; Yang, Q.-L.; Qiu, H.; Mei, T.-S. Acc. Chem. Res. 2020, 53, 300.
	(f) Ma, C.; Fang, P.; Liu, D.; Jiao, K.-J.; Gao, P.-S.; Qiu, H.; Mei, T.-S. Chem. Sci. 2021, 12, 12866.
	(g) Xu, C.; Lei, A.; Mei, T.-S.; Xu, H.-C.; Xu, K.; Zeng, C. CCS Chem. 2022, 4, 1120.
	(h) Gandeepan, P.; Finger, L. H.; Meyer, T. H.; Ackermann, L. Chem. Soc. Rev. 2020, 49, 4254.
	(i) Wang, Y.; Dana, S.; Long, H.; Xu, Y.; Li, Y.; Kaplaneris, N.; Ackermann, L. Chem. Rev. 2023, 123, 11269.
	(j) Lu, J.; Wang, Y.; McCallum, T.; Fu, N. iScience 2020, 23, 101796.
	(k) Wang, Z.; Ma, C.; Fang, P.; Xu, H.; Mei, T. Acta Chim. Sinica 2022, 80, 1115.
[6]	Fujishima, A.; Honda, K. Nature 1972, 238, 37.
[7]	Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; Mi, Q.; Santori, E. A.; Lewis, N. S. Chem. Rev. 2010, 110, 6446.
[8]	Hisatomi, T.; Kubota, J.; Domen, K. Chem. Soc. Rev. 2014, 43, 7520.
[9]	Wu, H.-L.; Li, X.-B.; Tung, C.-H.; Wu, L.-Z. Adv. Sci. 2018, 5, 1700684.
[10]	Thalluri, S. M.; Bai, L.; Lv, C.; Huang, Z.; Hu, X.; Liu, L. Adv. Sci. 2020, 7, 1902102.
[11]	Kumar, B.; Llorente, M.; Froehlich, J.; Dang, T.; Sathrum, A.; Kubiak, C. P. Annu. Rev. Phys. Chem. 2012, 63, 541.
[12]	Chang, X.; Wang, T.; Yang, P.; Zhang, G.; Gong, J. Adv. Mater. 2019, 31, 1804710.
[13]	Xu, S.; Carter, E. A. Chem. Rev. 2018, 119, 6631.
[14]	Zhang, W.; Jin, Z.; Chen, Z. Adv. Sci. 2022, 9, 2105204.
[15]	Kim, J.; Jang, J.; Hilberath, T.; Hollmann, F.; Park, C. B. Nat. Synth. 2022, 1, 776.
[16]	Song, R.; Chi, H.; Ma, Q.; Li, D.; Wang, X.; Gao, W.; Wang, H.; Wang, X.; Li, Z.; Li, C. J. Am. Chem. Soc. 2021, 143, 13664.
[17]	Cha, H. G.; Choi, K.-S. Nat. Chem. 2015, 7, 328.
[18]	Li, T.; Kasahara, T.; He, J.; Dettelbach, K. E.; Sammis, G. M.; Berlinguette, C. P. Nat. Commun. 2017, 8, 390.
[19]	Tateno, H.; Miseki, Y.; Sayama, K. ChemElectroChem 2017, 4, 3283.
[20]	Tateno, H.; Miseki, Y.; Sayama, K. Chem. Commun. 2017, 53, 4378.
[21]	Tateno, H.; Iguchi, S.; Miseki, Y.; Sayama, K. Angew. Chem. Int. Ed. 2018, 57, 11238.
[22]	Zhang, L.; Liardet, L.; Luo, J.; Ren, D.; Grätzel, M.; Hu, X. Nat. Catal. 2019, 2, 366.
[23]	Wang, J.-H.; Li, X.-B.; Li, J.; Lei, T.; Wu, H.-L.; Nan, X.-L.; Tung, C.-H.; Wu, L-Z. Chem. Commun. 2019, 55, 10376.
[24]	Gong, M.; Kim, J. K.; Zhao, X.; Li, Y.; Zhang, J.; Huang, M.; Wu, Y. Green Chem. 2019, 21, 3615.
[25]	(a) Zhao, Y.; Deng, C.; Tang, D.; Ding, L.; Zhang, Y.; Sheng, H.; Ji, H.; Song, W.; Ma, W.; Cheng, C.; Zhao, J. Nat. Catal. 2021, 4, 684.
	(b) Zhao, Y.; Duan, M.; Deng, C.; Yang, J.; Yang, S.; Zhang, Y.; Sheng, H.; Li, Y.; Chen, C.; Zhao, J. Nat. Commun. 2023, 14, 1943.
[26]	Wang, J.; Li, S.; Yang, C.; Gao, H.; Zuo, L.; Guo, Z.; Yang, P.; Jiang, Y.; Li, J.; Wu, L.-Z.; Tang, Z. Nat. Commun. 2024, 15, 6907.
[27]	(a) Huang, H.; Steiniger, K. A.; Lambert, T. H. J. Am. Chem. Soc. 2022, 144, 12567.
	(b) Barham, J. P.; König, B. Angew. Chem. Int. Ed. 2020, 59, 11732.
	(c) Wu, S.; Kaur, J.; Karl, T. A.; Tian, X.; Barham, J. P. Angew. Chem. Int. Ed. 2022, 61, e202107811.
	(d) Liu, J.; Lu, L.; Wood, D.; Lin, S. ACS Cent. Sci. 2020, 6, 1317.
	(e) Yu, Y.; Guo, P.; Zhong, J.-S.; Yuan, Y.; Ye, K.-Y. Org. Chem. Front. 2020, 7, 131.
	(f) Grimaud, L.; Lakhdar, S.; Vitale, M. R. Curr. Opin. Electrochem. 2023, 40, 101307.
[28]	Moutet, J.-C.; Reverdy, G. Tetrahedron Lett. 1979, 20, 2389.
[29]	Moutet, J.-C.; Reverdy, G. J. Chem. Soc., Chem. Commun. 1982, 654.
[30]	Shukla, S. S.; Rusting, J. F. J. Phys. Chem. 1985, 89, 3353.
[31]	Yan, H.; Hou, Z.-W.; Xu, H.-C. Angew. Chem. Int. Ed. 2019, 58, 4592.
[32]	Matsui, J. K.; Primer, D. N.; Molander, G. A. Chem. Sci. 2017, 8, 3512.
[33]	Hou, Z.-W.; Xu, H.-C. ChemElectroChem 2021, 8, 1571.
[34]	Wang, F.; Stahl, S. S. Angew. Chem. Int. Ed. 2019, 58, 6385.
[35]	Zhang, W.; Carpenter, K. L.; Lin, S. Angew. Chem. Int. Ed. 2020, 59, 409.
[36]	(a) Huang, H.; Strater, Z. M.; Rauch, M.; Shee, J.; Sisto, T. J.; Nuckolls, C.; Lambert, T. H. Angew. Chem. Int. Ed. 2019, 58, 13318.
	(b) Huang, H.; Lambert, T. H. Angew. Chem. Int. Ed. 2021, 60, 11163.
[37]	(a) Huang, H.; Lambert, T. H. J. Am. Chem. Soc. 2021, 143, 7247.
	(b) Huang, H.; Lambert, T. H. J. Am. Chem. Soc. 2022, 144, 18803.
[38]	(a) Huang, H.; Strater, Z. M.; Lambert, T. H. J. Am. Chem. Soc. 2020, 142, 1698.
	(b) Shen, T.; Lambert, T. H. J. Am. Chem. Soc. 2021, 143, 8597.
[39]	(a) Shen, T.; Lambert, T. H. Science 2021, 371, 620.
	(b) Shen, T.; Li, Y.-L.; Ye, K.-Y.; Lambert, T. H. Nature 2023, 614, 275.
[40]	Kim, H.; Kim, H.; Lambert, T. H.; Lin, S. J. Am. Chem. Soc. 2020, 142, 2087.
[41]	Cowper, N. G. W.; Chernowsky, C. P.; Williams, O. P.; Wickens, Z. K. J. Am. Chem. Soc. 2020, 142, 2093.
[42]	Chen, Y.-J.; Deng, W.-H.; Guo, J.-D.; Ci, R.-N.; Zhou, C.; Chen, B.; Li, X.-B.; Guo, X.-N.; Liao, R.-Z.; Tung, C.-H.; Wu, L.-Z. J. Am. Chem. Soc. 2022, 144, 17261.
[43]	Chen, Y.-J.; Lei, T.; Hu, H.-L.; Wu, H.-L.; Zhou, S.; Li, X.-B.; Chen, B.; Tung, C.-H.; Wu, L.-Z. Matter 2021, 4, 2354.
[44]	Aman, H.; Chang, R.; Ye, J. ChemCatChem 2024, 16, e202400635.
[45]	(a) Wang, F.; Chen, P.; Liu, G. Acc. Chem. Res. 2018, 51, 2036.
	(b) Gu, Q.-S.; Li, Z.-L.; Liu, X.-Y. Acc. Chem. Res. 2020, 53, 170.
	(c) Fu, G. C. ACS Cent. Sci. 2017, 3, 692.
[46]	Abderrazak, Y.; Bhattacharyya, A.; Reiser, O. Angew. Chem. Int. Ed. 2021, 60, 21100.
[47]	Li, L.; Yao, Y.; Fu, N. Chem. Catal. 2024, 4, 100898.
[48]	Liu, J.; Lu, L.; Wood, D.; Lin, S. ACS Cent. Sci. 2020, 6, 1317.
[49]	Barham, J. P.; Konig, B. Angew. Chem. Int. Ed. 2020, 59, 11732.
[50]	Huang, H.; Steiniger, K. A.; Lambert, T. H. J. Am. Chem. Soc. 2022, 144, 12567.
[51]	Wu, S.; Kaur, J.; Karl, T. A.; Tian, X.; Barham, J. P. Angew. Chem. Int. Ed. 2022, 61, e202107811.
[52]	Yang, G.; Wang, Y.; Qiu, Y. Chin. J. Org. Chem. 2021, 41, 3935 (in Chinese).
	杨光, 王衍伟, 仇友爱, 有机化学, 2021, 41, 3935.)
[53]	Ye, Z.; Liu, H.; Zhang, F. 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.)
[54]	Qiu, Y.; Scheremetjew, A.; Finger, L. H.; Ackermann, L. Chem.-Eur. J. 2020, 26, 3241.
[55]	Capaldo, L.; Quadri, L. L.; Merli, D.; Ravelli, D. Chem. Commun. 2021, 57, 4424.
[56]	Bi, H.; Zhou, Y.; Jiang, W.; Liu, J. Adv. Synth. Catal. 2022, 364, 1732.
[57]	(a) Tsurugi, H.; Mashima, K. J. Am. Chem. Soc. 2021, 143, 7879.
	(b) Chang, L.; An, Q.; Duan, L.; Feng, K.; Zuo, Z. Chem. Rev. 2022, 122, 2429.
[58]	Lai, X.-L.; Shu, X.-M.; Song, J.; Xu, H.-C. Angew. Chem. Int. Ed. 2020, 59, 10626.
[59]	Wang, M.; Wang, D.; Xu, K.; Zeng, C. Catal. Sci. Technol. 2024, 14, 1037.
[60]	(a) de Groot, L. H. M.; ilic, A.; Schwarz, J.; Wärnmark, K. J. Am. Chem. Soc. 2023, 145, 9369.
	(b) Li, Z.; Wang, X.; Xia, S.; Jin, J. Org. Lett. 2019, 21, 4259.
[61]	Niu, K.; Zhou, P.; Ding, L.; Hao, Y.; Liu, Y.; Song, H.; Wang, Q. ACS Sustainable Chem. Eng. 2021, 9, 16820.
[62]	(a) Hu, A.; Guo, J.-J.; Pan, H.; Zuo, Z. Science 2018, 361, 668.
	(b) An, Q.; Wang, Z.; Chen, Y.; Wang, X.; Zhang, K.; Pan, H.; Liu, W.; Zuo, Z. J. Am. Chem. Soc. 2020, 142, 6216.
[63]	Tan, Z.; He, X.; Xu, K.; Zeng, C. ChemSusChem 2022, 15, e202102360.
[64]	Jiang, Y.; Xu, K.; Zeng, C. CCS Chem. 2022, 4, 1796.
[65]	Morcillo, S. P. Angew. Chem. Int. Ed. 2019, 58, 14044.
[66]	Yang, Z.; Yang, D.; Zhang, J.; Tan, C.; Li, J.; Wang, S.; Zhang, H.; Huang, Z.; Lei, A. J. Am. Chem. Soc. 2022, 144, 13895.
[67]	Xu, P.; Chen, P.-Y.; Xu, H.-C. Angew. Chem. Int. Ed. 2020, 59, 14275.
[68]	(a) Cao, Y.; Huang, C.; Lu, Q. Nat. Synth. 2024, 3, 537.
	(b) Wang, M.; Huang, Y.; Hu, P. Science 2024, 383, 537.
[69]	(a) Ye, K.-Y.; Pombar, G.; Fu, N.; Sauer, G. S.; Keresztes, I.; Lin, S. J. Am. Chem. Soc. 2018, 140, 2438.
	(b) Song, L.; Fu, N.; Ernst, B. G.; Lee, W. H.; Frederick, M. O.; DiStasio, R. A. Jr.; Lin, S. Nat. Chem. 2020, 12, 747.
[70]	Song, L.; Fu, N.In Comprehensive Organometallic Chemistry IV, Eds.: ParkinG.; MeyerK.; O'hare,D., Elsevier, 2022, Vol. 13, pp. 339-403.
[71]	Niu, L.; Jiang, C.; Liang, Y.; Liu, D.; Bu, F.; Shi, R.; Chen, H.; Chowdhury, A. D.; Lei, A. J. Am. Chem. Soc. 2020, 142, 17693.
[72]	Fu, N.; Sauer, G. S.; Saha, A.; Loo, A.; Lin, S. Science 2017, 357, 575.
[73]	Wang, Y.; Li, L.; Fu, N. ACS Catal. 2022, 12, 10661.
[74]	Lai, X.-L.; Chen, M.; Wang, Y.; Song, J.; Xu, H.-C. J. Am. Chem. Soc. 2022, 144, 20201.
[75]	Yuan, Y.; Yang, J.; Zhang, J. Chem. Sci. 2023, 14, 705.
[76]	Yang, K.; Wang, Y.; Luo, S.; Fu, N. Chem.-Eur. J. 2023, 29, e202203962.
[77]	(a) Wang, D.; Zhu, N.; Chen, P.; Lin, Z.; Liu, G. J. Am. Chem. Soc. 2017, 139, 15632.
	(b) Fu, N.; Song, L.; Liu, J.; Shen, Y.; Siu, J. C.; Lin, S. J. Am. Chem. Soc. 2019, 141, 14480.
[78]	Cai, C.-Y.; Lai, X.-L.; Wang, Y.; Hu, H.-H.; Song, J.; Yang, Y.; Wang, C.; Xu, H.-C. Nat. Catal. 2022, 5, 943.
[79]	Fan, W.; Zhao, X.; Deng, Y.; Chen, P.; Wang, F.; Liu, G. J. Am. Chem. Soc. 2022, 144, 21674.
[80]	Zhang, W.; Wang, F.; McCann, S. D.; Wang, D.; Chen, P.; Stahl, S. S.; Liu, G. Science 2016, 353, 1014.
[81]	Lai, X.-L.; Xu, H.-C. J. Am. Chem. Soc. 2023, 145, 18753.
[82]	Zhang, R.; Li, L.; Zhou, K.; Fu, N. Chem.-Eur. J. 2023, 29, e202301034.
[83]	Mo, Y.; Lu, Z.; Rughoobur, G.; Patil, P.; Gershenfeld, N.; Akin-wande, A. I.; Buchwald, S. L.; Jensen, K. F. Science 2020, 368, 1352.
[84]	Li, L.; Fu, N. Synlett 2023, 34, 1549.
[85]	Yang, K.; Lu, J.; Li, L.; Luo, S.; Fu, N. Chem.-Eur. J. 2022, 28, e202202370.
[86]	Xue, P.; Li, L.; Fu, N. Org. Lett. 2022, 24, 7595.
[87]	Kullmer, C. N. P.; Kautzky, J. A.; Krska, S. W.; Nowak, T.; Dreher, S. D.; MacMillan, D. W. C. Science 2022, 376, 532.
[88]	Lu, J.; Yao, Y.; Li, L.; Fu, N. J. Am. Chem. Soc. 2023, 145, 26774.
[89]	Zou, L.; Wang, X.; Xiang, S.; Zheng, W.; Lu, Q. Angew. Chem., Int. Ed. 2023, 62, e202301026.
[90]	Zou, L.; Xiang, S.; Sun, R.; Lu, Q. Nat. Commun. 2023, 14, 7992.
[91]	Zou, L.; Zheng, X.; Yi, X.; Lu, Q. Nat. Commun. 2024, 15, 7826.
[92]	Wang, L.; Huo, X.; He, X.; Ackermann, L.; Wang, D. Green Chem. 2024, 26, 8315.
[93]	Huang, L.; Ji, T.; Rueping, M. J. Am. Chem. Soc. 2020, 142, 3532.
[94]	Zou, L.; Sun, R.; Tao, Y.; Wang, X.; Zheng, X.; Lu, Q. Nat. Commun. 2024, 15, 5245.
[95]	Liu, Z.-R.; Zhu, X.-Y.; Guo, J.-F.; Ma, C.; Zuo, Z.; Mei, T.-S. Sci. Bull. 2024, 69, 1866.
[96]	Li, W.; Zhang, R.; Zhou, N.; Lu, J.; Fu, N. Chem. Commun. 2024, 60, 11714.
[97]	Xiong, P.; Ivlev, S. I.; Meggers, E. Nat. Catal. 2023, 6, 1186.

光电化学金属催化研究进展