电驱动硫化学合成研究进展

doi:10.6023/cjoc202604034

摘要/Abstract

有机硫分子,广泛出现于药物化学、功能材料、能源转储。硫,广泛的多价态（-2、0、+2、+4、+6）赋予其独特的氧化还原特性,令其合成高度依赖氧化还原的精准调控。传统方法依赖过氧化物、高价碘等非绿色氧化剂,存在原子经济性低、过度氧化、副产物污染等瓶颈。电催化以电子为绿色氧化还原试剂,通过电压、电流、电极、电解质精准调控电子转移速率与路径,实现硫原子价态的精准调控转化,兼具绿色、环保、安全、高选择性与高原子经济性。本文,围绕电催化绿色氧化还原催化模式,系统梳理电驱动硫化学的各类合成策略,归纳总结相关研究进展,并深入剖析其反应作用机制。

关键词: 硫化学, 电化学, 电氧化还原

Organic sulfur compounds are widely used in medicinal chemistry, asymmetric catalysis, and functional materials. The unique multivalent redox properties of sulfur atoms (-2, 0, +2, +4, +6) make their synthesis highly dependent on precise redox regulation. Traditional methods rely on hazardous oxidants such as peroxides and hypervalent iodine, suffering from low atom economy, over-oxidation, and byproduct contamination. Electrocatalysis employs electrons as green redox reagents, enabling stepwise and controllable transformation of sulfur valence states by precisely regulating electron transfer rates and pathways through potential, current, electrodes, and media, offering a green, safe, highly selective, and atom-economical approach. This article focuses on the electrocatalytic green redox catalysis mode, systematically sorts out various synthetic strategies of electro-driven sulfur chemistry, summarizes the related research progress, and deeply analyzes its reaction mechanism.

Key words: Sulfur Chemistry, Electrochemistry, Electroredox

引用此文

张象金, 姜雪峰. 电驱动硫化学合成研究进展[J]. 有机化学, doi: 10.6023/cjoc202604034.

Zhang Xiangjin, Jiang Xuefeng. Research Progress on Electro-Driven Sulfur Chemistry Synthesis[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202604034.

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参考文献

[1] (a) Wang, M.; Jiang, X. Top. Curr. Chem. 2018, 376, 14. (b) Huang, S.; Wang, M.; Jiang, X. Chem. Soc. Rev. 2022, 51, 8351-8377. (c) Narayan, M.; Welker, E.; Wedemeyer, W. J.; Scheraga, H. D. Acc. Chem. Res. 2000, 33, 805–812. (d) Lee, M. H.; Yang, Z.; Lim, C. W.; Lee, Y. H.; Dongbang, S.; Kang, C.; Kim, J. S. Chem. Rev. 2013, 113, 5071–5109. (e) Zuo, S.; Liu, T.; Li, L.; Xu, H.; Guo, J.; Wang, Q.; Yang, Y.; He, Z.; Sun, J.; Sun, B. Cell Rep. Med. 2024, 5, 101432. (f) Jiang, C.-S.; Müller, W. E. G.; Schröder, H. C.; Guo, Y.-W. Chem. Rev. 2011, 112, 2179-2207.
[2] (a) Chalker, J. M.; Worthington, M. J. H.; Lundquist, N. A.; Esdaile, L. J. Top. Curr. Chem. 2019, 377, 14. (b) Meng, J.; Jiang, X. Sci. Sin. Chim. 2025, 55, 1113 (in Chinese). (孟娇龙, 姜雪峰, 中国科学: 化学, 2025, 55, 1113.). (c) Mazumder, K.; Voit, B.; Banerjee, S. ACS Omega 2024, 9, 6253-6279.
[3] (a) Song, H.; Meng, J.; Jiang, X. Natl. Sci. Rev. 2025, 12, nwaf475. (b) Ye, H.; Li, M.; Liu, T.; Li, Y.; Lu, J. ACS Energy Letters 2020, 5, 2234-2245. (c) Yoshida, J.; Kataoka, K.; Horcajada, R.; Nagaki, A. Chem. Rev. 2008, 108, 2265–2299.
[4] Block, E.; Bayer, T.; Naganathan, S.; Zhao, S.-H. J. Am. Chem. Soc. 1996, 118, 2799–2810.
[5] Yoshida, J.; Kataoka, K.; Horcajada, R.; Nagaki, A. Chem. Rev. 2008, 108, 2265–2299.
[6] (a) Amri, N.; Wirth, T. Chem. Rec. 2021, 21, 2526-2537. (b) Lei, Z.-L.; Tang, H.-T.; Pan, Y.-M. Green Chem. 2025, 27, 15442-15461.
[7] Yang, Z.; Shi, W.; Alhumade, H.; Yi, H.; Lei, A. Nat. Synth. 2023, 2, 217-230.
[8] Sushma, C.; Pramanik, R.; Barathkumar, J.; Nagarajan, S. Asian J. Org. Chem. 2025, 14, e00388.
[9] Wang, M.; Jiang, X. ACS Sustainable Chem. Eng. 2022, 10, 671-677.
[10] (a) Ye, Z.; Zhang, X.; Ma, W.; Zhang, F. Green Chem. 2023, 25, 2524-2540. (b) Huang, J.; Li, X.; Xu, L.; Wei, Y. Org. Chem. Front. 2025, 12, 3454-3461. (c) Wang, S.; Zhi, S.; Cai, T.; Li, D.; Xu, B.; Yang, Y.; Hu, Y.; Zhang, J.; Qiao, Z.; Yuan, M.; Jin, Y. J. Org. Chem. 2025, 90, 17952-17965. (d) Song, X.; Yang, Z.; Yin, W.; Li, X.; Qian, L.; Jin, Y.; Yang, M. J. Org. Chem. 2025, 90, 13253-13261. (e) Li, L.; Li, Y.; Hu, J.; Yang, C.; Sun, J.; Qian, P. J. Org. Chem. 2025, 90, 15313-15323. (f) Wu, M.; Chen, M.; Wang, W.; Liu, P.; Sun, P. J. Org. Chem. 2025, 90, 7351-7358.
[11] Laudadio, G.; Straathof, N. J. W.; Lanting, M. D.; Knoops, B.; Hessel, V.; Noël, T. Green Chem. 2017, 19, 4061-4066.
[12] Park, J. K.; Lee, S. J. Org. Chem. 2021, 86, 13790-13799.
[13] Yang, Z.; Shi, Y.; Zhan, Z.; Zhang, H.; Xing, H.; Lu, R.; Zhang, Y.; Guan, M.; Wu, Y. ChemElectroChem 2018, 5, 3619-3623.
[14] Zhang, X.; Cui, T.; Zhang, Y.; Gu, W.; Liu, P.; Sun, P. Adv. Synth. Catal. 2019, 361, 2014-2019.
[15] Laudadio, G.; Barmpoutsis, E.; Schotten, C.; Struik, L.; Govaerts, S.; Browne, D. L.; Noël, T. J. Am. Chem. Soc. 2019, 141, 5664-5668.
[16] Wang, H.; Yu, M.; Zhang, P.; Wan, H.; Cong, H.; Lei, A. Sci. Bull. 2022, 67, 79-84.
[17] Zhou, P.; Niu, K.; Song, H.; Liu, Y.; Wang, Q. Green Chem. 2022, 24, 5760-5763.
[18] Klein, M.; Waldvogel, S. R. Angew. Chem. Int. Ed. 2021, 60, 23197-23201.
[19] Kong, X.; Lin, L.; Chen, X.; Chen, Y.; Wang, W.; Xu, B. ChemSusChem 2021, 14, 3277-3282.
[20] Li, X.; Huang, J.; Xu, L.; Liu, J.; Wei, Y. Adv. Synth. Catal. 2023, 365, 4647-4653.
[21] Li, Y.; Wen, L.; Guo, W. Chem. Soc. Rev. 2023, 52, 1168-1188.
[22] Bilal, M.; Liu, X.-B.; Liang, Y.-F. Tetrahedron Chem 2025, 15, 100141.
[23] Jang, H.-Y. Org. Biomol. Chem. 2021, 19, 8656-8686.
[24] Mulina, O. M.; Ilovaisky, A. I.; Terent'ev, A. O. Eur. J. Org. Chem. 2018, 2018, 4648-4672.
[25] Hu, X.; Zhong, K.; Ruan, Z. Chem. Commun. 2024, 60, 8573-8576.
[26] Kuzmin, J.; Röckl, J.; Schwarz, N.; Djossou, J.; Ahumada, G.; Ahlquist, M.; Lundberg, H. Angew. Chem. Int. Ed. 2023, 62, e202304272.
[27] Pople, J. M. M.; Nicholls, T. P.; Pham, L. N.; Bloch, W. M.; Lisboa, L. S.; Perkins, M. V.; Gibson, C. T.; Coote, M. L.; Jia, Z.; Chalker, J. M. J. Am. Chem. Soc. 2023, 145, 11798-11810.
[28] Krumbiegel, C.; Breitschaft, F. A.; Waldvogel, S. R. Chem. Commun. 2025, 61, 11267-11270.
[29] Sun, F.; Liu, X.; Chen, X.; Qian, C.; Ge, X. Chin. J. Org. Chem. 2017, 37, 2211-2220 (in Chinese). (孙丰莉, 刘学民, 陈新志, 钱超, 葛新, 有机化学, 2017, 37, 2211-2220.)
[30] Bu, F.; Deng, Y.; Shi, P.; Huang, R.; Tan, J.; Li, H.; Chen, Y.; Lei, A.; Li, W. J. Am. Chem. Soc. 2026, 148, 7322-7332.
[31] Strehl, J.; Hilt, G. Eur. J. Org. Chem. 2021, 2022, 35-39.
[32] Ang, N. W. J.; Ackermann, L. Chem. Eur. J. 2021, 27, 4883-4887.
[33] Kong, Z.; Pan, C.; Li, M.; Wen, L.; Guo, W. Green Chem. 2021, 23, 2773-2777.
[34] Lou, T. S. B.; Kawamata, Y.; Ewing, T.; Correa-Otero, G. A.; Collins, M. R.; Baran, P. S. Angew. Chem. Int. Ed. 2022, 61, e202208080.
[35] Xu, Z.; Zhou, Z.; Wang, X.; Yang, Y.; Pan, Y.; Wang, Y. Green Chem. 2026, 28, 120-131.
[36] (a) Xiao, X.; Feng, M.; Jiang, X. Angew. Chem. Int. Ed. 2016, 55, 14121–14125. (a) Xiao, X.; Xue, J.; Jiang, X. Nat. Commun. 2018, 9, 2191–2200. (a) Xue, J.; Jiang, X. Nat. Commun. 2020, 11, 2191–2199. (a) Yu, Q.; Zhang, X.; Jiang, X. Angew. Chem. Int. Ed. 2024, e202408158. (a) Huang, S.; Zeng, D., Wang. M.; Jiang, X. Nat. Synth. 2026, 5, 398-408.
[37] Zhang, X.; Bai, L.; Li, C.; Bai, L.; Jiang, X. J. Am. Chem. Soc. 2026, 148, 12793-12804.
[38] Wang, Z.; Ma, C.; Fang, P.; Xu, H.; Mei, T. Acta Chim. Sinica 2022, 80, 1115-1134 (in Chinese). (王振华, 马聪, 方萍, 徐海超, 梅天胜, 化学学报, 2022, 80, 1115-1134.)
[39] Francke, R.; Little, R. D. Chem. Soc. Rev. 2014, 43, 2492–2521.
[40] Bai, L.; Jiang, X. CCS Chem. 2025, 7, 1889–1902.
[41] Huang, P.; Wang, P.; Tang, S., Fu, Z.; Lei, A. Angew. Chem. Int. Ed. 2018, 57, 8115–8119.
[42] Liu, D.; Ma, H. X.; Fang, P.; Mei, T. S. Angew. Chem. Int. Ed. 2019, 58, 5033-5037.
[43] Kang, J.-C.; Li, Z.-H.; Chen, C.; Dong, L.-K.; Zhang, S.-Y. J. Org. Chem. 2021, 86, 15326-15334.
[44] Wang, D.-Y.; Si, Y.; Guo, W.; Fu, Y. Nat. Commun. 2021, 12, 3220.
[45] Fährmann, J.; Hilt, G. Chem. Eur. J. 2021, 27, 11141-11149.
[46] Li, Y.; Wang, H.; Wang, Z.; Alhumade, H.; Huang, Z.; Lei, A. Chem. Sci. 2023, 14, 372-378.
[47] Fu, M.-Q.-H.; He, Y.-H.; Guan, Z. Org. Chem. Front. 2024, 11, 6790-6796.
[48] Chen, H.; Yin, Y.; Wang, G.; Xiao, X.; Jiang, X.; Feng, M. Angew. Chem. Int. Ed. 2025, 64, e202512612.