Citation: Dengke Ma, Youai Qiu. Electrochemical strategies for advancing enantioselective enamine catalysis[J]. Chinese Chemical Letters, ;2026, 37(4): 111892. doi: 10.1016/j.cclet.2025.111892 shu

Electrochemical strategies for advancing enantioselective enamine catalysis

Dengke Ma ^{a, *,} ,
Youai Qiu ^{b, *,}

a.
School of Pharmaceutical Sciences, Capital Medical University, Beijing 100069, China
b.
State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, Haihe Laboratory of Sustainable Chemical Transformations, College of Chemistry, Nankai University, Tianjin 300071, China

madk@ccmu.edu.cn

qiuyouai@nankai.edu.cn

Received Date: 25 June 2025
Revised Date: 3 September 2025
Accepted Date: 24 September 2025
Available Online: 24 September 2025

Figures(19)

Enantioselective enamine catalysis has enriched asymmetric synthesis by enabling precise stereochemical control. While classically thermal/photochemical strategies have expanded reaction diversity, electrochemical enantiocontrol remains underexplored despite its potential for tunable redox manipulation. This review systematically evaluates electrochemical enantioselective enamine catalysis through polar/radical mediated chemical bond formation pathways, aiming to delineate current mechanistic paradigms and highlight electrochemistry's unique role on asymmetric enamine catalysis beyond thermodynamic and photochemical conditions. Future efforts including developing enhanced compatibility of chiral catalysts and intermediates with electrochemical systems, as well as exploiting transformative techniques for mechanistic elucidation could be promising to unlock more novel transformations and stereoselectivity models.
- Electrochemistry,
- Asymmetric catalysis and synthesis,
- Enamine catalysis,
- Stereocontrol,
- Radical chemistry
1. [1]
  C.C.C. Johansson, T.J. Colacot, Angew. Chem. Int. Ed. 49 (2010) 676–707. doi: 10.1002/anie.200903424
2. [2]
  A.M.R. Smith, K.K. Hii, Chem. Rev. 111 (2011) 1637–1656. doi: 10.1021/cr100197z
3. [3]
  S. Liang, K. Xu, C.C. Zeng, et al., Adv. Synth. Catal. 360 (2018) 4266–4292. doi: 10.1002/adsc.201800519
4. [4]
  L. Zhu, D. Wang, Z. Jia, et al., ACS. Catal. 8 (2018) 5466–5484. doi: 10.1021/acscatal.8b01263
5. [5]
  B. List, Acc. Chem. Res. 37 (2004), 548–557. doi: 10.1021/ar0300571
6. [6]
  W. Notz, F. Tanaka, C.F. Barbas, Acc. Chem. Res. 37 (2004) 580–591. doi: 10.1021/ar0300468
7. [7]
  S. Mukherjee, J.W. Yang, S. Hoffmann, et al., Chem. Rev. 107 (2007) 5471–5569. doi: 10.1021/cr0684016
8. [8]
  P. Melchiorre, M. Marigo, A. Carlone, et al., Angew. Chem. Int. Ed. 47 (2008) 6138–6171. doi: 10.1002/anie.200705523
9. [9]
  L. Xu, J. Luo, Y. Lu, Chem. Commun. 2009 (2009) 1807–1821. doi: 10.1039/b821070e
10. [10]
  S. Bertelsen, K.A. Jørgensen, Chem. Soc. Rev. 38 (2009) 2178–2189. doi: 10.1039/b903816g
11. [11]
  A. Quintard, S. Belot, E. Marchal, et al., Eur. J. Org. Chem. 2010 (2010) 927–936. doi: 10.1002/ejoc.200901283
12. [12]
  M. Nielsen, D. Worgull, T. Zweifel, et al., Chem. Commun. 47 (2011) 632–649. doi: 10.1039/C0CC02417A
13. [13]
  K.L. Jensen, G. Dickmeiss, H. Jiang, et al., Acc. Chem. Res. 45 (2012) 248–264. doi: 10.1021/ar200149w
14. [14]
  T. Kano, K. Maruoka, Chem. Sci. 4 (2013) 907–915. doi: 10.1039/C2SC21612D
15. [15]
  B.M. Paz, H. Jiang, K.A. Jorgensen, Chem. Eur. J. 21 (2015) 1846–1853. doi: 10.1002/chem.201405038
16. [16]
  S. Meninno, C. Volpe, A. Lattanzi, ChemCatChem. 11 (2019) 3716–3729. doi: 10.1002/cctc.201900569
17. [17]
  T.D. Beeson, A. Mastracchio, J. -B. Hong, et al., Science 316 (2007) 582–585. doi: 10.1126/science.1142696
18. [18]
  M. Mečiarová, P. Tisovský, R. Šebesta, New J. Chem. 40 (2016) 4855–4864. doi: 10.1039/C6NJ00079G
19. [19]
  Y.Q. Zou, F.M. Hörmann, T. Bach, Chem. Soc. Rev. 47 (2018) 278–290. doi: 10.1039/c7cs00509a
20. [20]
  D. Ma, T.H.F. Wong, P. Melchiorre, Asymmetric photoredox reactions without photocatalysts, in: T. Akiyama, I. Ojima (Eds.), Catalytic Asymmetric Synthesis, 4th ed., John Wiley & Sons, Inc., Hoboken, 2022, pp. 329–354.
21. [21]
  D.A. Nicewicz, D.W.C. MacMillan, Science 322 (2008) 77–80. doi: 10.1126/science.1161976
22. [22]
  D.A. Nagib, M.E. Scott, D.W.C. MacMillan, J. Am. Chem. Soc. 131 (2009) 10875–10877. doi: 10.1021/ja9053338
23. [23]
  H.W. Shih, M.N. Vander Wal, R.L. Grange, et al., J. Am. Chem. Soc. 132 (2010) 13600–13603. doi: 10.1021/ja106593m
24. [24]
  M. Neumann, S. Füldner, B. König, et al., Angew. Chem. Int. Ed. 50 (2011) 951–954. doi: 10.1002/anie.201002992
25. [25]
  Y. Zhu, L. Zhang, S. Luo, J. Am. Chem. Soc. 136 (2014) 14642–14645. doi: 10.1021/ja508605a
26. [26]
  E. Arceo, I.D. Jurberg, A. Álvarez-Fernández, et al., Nat. Chem. 5 (2013) 750–756. doi: 10.1038/nchem.1727
27. [27]
  M. Silvi, E. Arceo, I.D. Jurberg, et al., J. Am. Chem. Soc. 137 (2015) 6120–6123. doi: 10.1021/jacs.5b01662
28. [28]
  A. Bahamonde, P. Melchiorre, J. Am. Chem. Soc. 138 (2016) 8019–8030. doi: 10.1021/jacs.6b04871
29. [29]
  G. Filippini, M. Silvi, P. Melchiorre, Angew. Chem. Int. Ed. 56 (2017) 4447–4451. doi: 10.1002/anie.201612045
30. [30]
  E.J. Horn, B.R. Rosen, P.S. Baran, ACS Cent. Sci. 2 (2016) 302–308. doi: 10.1021/acscentsci.6b00091
31. [31]
  M. Yan, Y. Kawamata, P.S. Baran, Chem. Rev. 117 (2017) 13230–13319. doi: 10.1021/acs.chemrev.7b00397
32. [32]
  Y. Jiang, K. Xu, C. Zeng, Chem. Rev. 118 (2018) 4485–4540. doi: 10.1021/acs.chemrev.7b00271
33. [33]
  J. -i. Yoshida, A. Shimizu, R. Hayashi, Chem. Rev. 118 (2018) 4702–4730. doi: 10.1021/acs.chemrev.7b00475
34. [34]
  T.H. Meyer, I. Choi, C. Tian, et al., Chem. 6 (2020) 2484–2496. doi: 10.1016/j.chempr.2020.08.025
35. [35]
  C. Zhu, N.W.J. Ang, T.H. Meyer, et al., ACS Cent. Sci. 7 (2021) 415–431. doi: 10.1021/acscentsci.0c01532
36. [36]
  L.F.T. Novaes, J.J. Liu, Y.F. Shen, et al., Chem. Soc. Rev. 50 (2021) 7941–8002. doi: 10.1039/d1cs00223f
37. [37]
  X. Cheng, A.W. Lei, T. -S. Mei, et al., CCS Chem. 4 (2022) 1120–1152. doi: 10.31635/ccschem.021.202101451
38. [38]
  Q.L. Zhang, K. Liang, C. Guo, Sci. China Chem. 67 (2024) 755–758. doi: 10.1007/s11426-023-1832-7
39. [39]
  W. Zeng, Y. Wang, C. Peng, et al., Chem. Soc. Rev. 54 (2025) 4468–4501. doi: 10.1039/d4cs01142b
40. [40]
  J. Zhong, Y. Yu, D. Zhang, et al., Chin. Chem. Lett. 32 (2021) 963–972. doi: 10.1016/j.cclet.2020.08.011
41. [41]
  W. Zhou, X. Chen, L. Lu, et al., Chin. Chem. Lett. 35 (2024) 08902.
42. [42]
  P.Y. Chen, C. Huang, L.H. Jie, et al., J. Am. Chem. Soc. 146 (2024) 7178–7184. doi: 10.1021/jacs.4c00878
43. [43]
  P. Zhou, T. Zou, H.J. Song, et al., Chin. Chem. Lett. 37 (2026) 111673. doi: 10.1016/j.cclet.2025.111673
44. [44]
  S. Rani, N. Sbei, S. Rahali, et al., Chin. Chem. Lett. 36 (2025) 111216. doi: 10.1016/j.cclet.2025.111216
45. [45]
  Q. Lin, L. Li, S. Luo, Chem. Eur. J. 25 (2019) 10033–10044. doi: 10.1002/chem.201901284
46. [46]
  M. Ghosh, V.S. Shinde, M. Rueping, Beilstein J. Org. Chem. 15 (2019) 2710–2746. doi: 10.3762/bjoc.15.264
47. [47]
  C. Margarita, H. Lundberg, Catalysts. 10 (2020) 982. doi: 10.3390/catal10090982
48. [48]
  X. Chang, Q. Zhang, C. Guo, Angew. Chem. Int. Ed. 59 (2020) 12612–12622. doi: 10.1002/anie.202000016
49. [49]
  K.J. Jiao, Z.H. Wang, C. Ma, et al., Chem. Catal. 2 (2022) 3019–3047.
50. [50]
  F. Medici, S. Resta, S. Andolina, et al., Catalysts. 13 (2023) 944. doi: 10.3390/catal13060944
51. [51]
  J. Rein, S.B. Zacate, K. Mao, et al., Chem. Soc. Rev. 52 (2023) 8106–8125. doi: 10.1039/d3cs00511a
52. [52]
  C. Gao, X. Liu, M. Wang, et al., Chin. J. Org. Chem. 44 (2024) 673–727. doi: 10.6023/cjoc202402005
53. [53]
  X. Jiang, C. Zou, W. Zhuang, et al., Green. Chem. 27 (2025) 915–945. doi: 10.1039/d4gc05316h
54. [54]
  Z. -H. Wang, P. -S. Gao, X. Wang, et al., J. Am. Chem. Soc. 143 (2021) 15599–15605. doi: 10.1021/jacs.1c08671
55. [55]
  D. Mazzarella, C. Qi, M. Vanzella, et al., Angew. Chem. Int. Ed. 63 (2024) e202401361. doi: 10.1002/anie.202401361
56. [56]
  K.L. Jensen, P.T. Franke, L.T. Nielsen, et al., Angew. Chem. Int. Ed. 49 (2010) 129–133. doi: 10.1002/anie.200904754
57. [57]
  N. Fu, L. Li, Q. Yang, et al., Org. Lett. 19 (2017) 2122–2125. doi: 10.1021/acs.orglett.7b00746
58. [58]
  X. Liu, S. Sun, Z. Meng, et al., Org. Lett. 17 (2015) 2396–2399. doi: 10.1021/acs.orglett.5b00909
59. [59]
  X. Liu, Z. Meng, C. Li, et al., Angew. Chem. Int. Ed. 54 (2015) 6012–6015. doi: 10.1002/anie.201500703
60. [60]
  G. Zhang, Y. Ma, S. Wang, et al., Chem. Sci. 4 (2013) 2645–2651. doi: 10.1039/c3sc50604e
61. [61]
  Q. Yang, L. Zhang, C. Ye, et al., Angew. Chem. Int. Ed. 56 (2017) 3694–3698. doi: 10.1002/anie.201700572
62. [62]
  H. Hou, S. Zhu, L. Atodiresei, et al., Eur. J. Org. Chem. 2018 (2018) 1277–1280. doi: 10.1002/ejoc.201800117
63. [63]
  F.Y. Lu, Y.J. Chen, Y. Chen, et al., Chem. Commun. 56 (2020) 623–626. doi: 10.1039/c9cc09178e
64. [64]
  X. Liu, X. Yan, J.H. Yu, et al., Org. Lett. 21 (2019) 5626–5629. doi: 10.1021/acs.orglett.9b01965
65. [65]
  C.L. Dong, X. Ding, L.Q. Huang, et al., Org. Lett. 22 (2020) 1076–1080. doi: 10.1021/acs.orglett.9b04613
66. [66]
  L. Li, Y. Li, N. Fu, et al., Angew. Chem. Int. Ed. 59 (2020) 14347–14351. doi: 10.1002/anie.202006016
67. [67]
  R. Francke, R.D. Little, Chem. Soc. Rev. 43 (2014) 2492–2521. doi: 10.1039/c3cs60464k
68. [68]
  J.E. Nutting, M. Rafiee, S.S. Stahl, Chem. Rev. 118 (2018) 4834–4885. doi: 10.1021/acs.chemrev.7b00763
69. [69]
  F. Wang, S.S. Stahl, Acc. Chem. Res. 53 (2020) 561–574. doi: 10.1021/acs.accounts.9b00544
70. [70]
  X. Yang, Z. Xie, Y. Li, et al., Chem. Sci. 11 (2020) 4741–4746. doi: 10.1039/d0sc00683a
71. [71]
  Y. Chen, Y. Wu, G. Wang, et al., Chin. Chem. Lett. 35 (2024) 109445. doi: 10.1016/j.cclet.2023.109445
72. [72]
  X.H. Ho, S.I. Mho, H. Kang, et al., Eur. J. Org. Chem. 2010 (2010) 4436–4441. doi: 10.1002/ejoc.201000453
73. [73]
  J.Y. He, N.N. Wang, R. Zhao, et al., Eur. J. Org. Chem. 27 (2024) e202400817. doi: 10.1002/ejoc.202400817
74. [74]
  F. Benfatti, M.G. Capdevila, L. Zoli, et al., Chem. Commun. 2009 (2009) 5919–5921. doi: 10.1039/b910185c
75. [75]
  B. Zhang, S.K. Xiang, L.H. Zhang, et al., Org. Lett. 13 (2011) 5212–5215. doi: 10.1021/ol202090a
76. [76]
  F. Huang, L. Xu, J. Xiao, Chin. J. Chem. 30 (2012) 2721–2725. doi: 10.1002/cjoc.201200850
77. [77]
  E. Larionov, M.M. Mastandrea, M.A. Pericàs, ACS. Catal. 7 (2017) 7008–7013. doi: 10.1021/acscatal.7b02659
78. [78]
  J.Y. He, C. Zhu, W.X. Duan, et al., Angew. Chem. Int. Ed. 63 (2024) e202401355. doi: 10.1002/anie.202401355
79. [79]
  Q. Lin, Y. Duan, Y. Li, et al., Nat. Commun. 15 (2024) 6900. doi: 10.1038/s41467-024-50945-2
80. [80]
  N.N. Bui, X.H. Ho, S.I. Mho, et al., Eur. J. Org. Chem. 2009 (2009) 5309–5312. doi: 10.1002/ejoc.200900871
81. [81]
  Y. Duan, Y. Zhang, J. Chen, et al., Angew. Chem. Int. Ed. (2025) e202505826. doi: 10.1002/anie.202505826
1. [1]
  Nianhua Luo , Jiayi Jiang , Muhammad Suleman , Zhaowen Liu , Shuping Huang , Wei Xiao , Jie Wu , Jiapian Huang . Advances in radical Smiles rearrangement. Chinese Chemical Letters, 2026, 37(2): 111556-. doi: 10.1016/j.cclet.2025.111556
2. [2]
  Xue Xin , Qiming Qu , Islam E. Khalil , Yuting Huang , Mo Wei , Jie Chen , Weina Zhang , Fengwei Huo , Wenjing Liu . Hetero-phase zirconia encapsulated with Au nanoparticles for boosting electrocatalytic nitrogen reduction. Chinese Chemical Letters, 2024, 35(5): 108654-. doi: 10.1016/j.cclet.2023.108654
3. [3]
  Zixuan Guo , Xiaoshuai Han , Chunmei Zhang , Shuijian He , Kunming Liu , Jiapeng Hu , Weisen Yang , Shaoju Jian , Shaohua Jiang , Gaigai Duan . Activation of biomass-derived porous carbon for supercapacitors: A review. Chinese Chemical Letters, 2024, 35(7): 109007-. doi: 10.1016/j.cclet.2023.109007
4. [4]
  Qiang Cao , Xue-Feng Cheng , Jia Wang , Chang Zhou , Liu-Jun Yang , Guan Wang , Dong-Yun Chen , Jing-Hui He , Jian-Mei Lu . Graphene from microwave-initiated upcycling of waste polyethylene for electrocatalytic reduction of chloramphenicol. Chinese Chemical Letters, 2024, 35(4): 108759-. doi: 10.1016/j.cclet.2023.108759
5. [5]
  Yuemin Chen , Yunqi Wu , Guoao Wang , Feihu Cui , Haitao Tang , Yingming Pan . Electricity-driven enantioselective cross-dehydrogenative coupling of two C(sp³)-H bonds enabled by organocatalysis. Chinese Chemical Letters, 2024, 35(9): 109445-. doi: 10.1016/j.cclet.2023.109445
6. [6]
  Li Li , Zhi-Xin Yan , Chuan-Kun Ran , Yi Liu , Shuo Zhang , Tian-Yu Gao , Long-Fei Dai , Li-Li Liao , Jian-Heng Ye , Da-Gang Yu . Electro-reductive carboxylation of CCl bonds in unactivated alkyl chlorides and polyvinyl chloride with CO₂. Chinese Chemical Letters, 2024, 35(12): 110104-. doi: 10.1016/j.cclet.2024.110104
7. [7]
  Yan-Jiang Li , Shu-Lei Chou , Yao Xiao . Detecting dynamic structural evolution based on in-situ high-energy X-ray diffraction technology for sodium layered oxide cathodes. Chinese Chemical Letters, 2025, 36(2): 110389-. doi: 10.1016/j.cclet.2024.110389
8. [8]
  Shuai Chen , Anzai Shi , Guoqing Yang , Pengfei Xie , Feng Liu , Youai Qiu . Electrochemical demethoxyl-cyanation of methoxyarenes via S_NAr. Chinese Chemical Letters, 2025, 36(9): 110810-. doi: 10.1016/j.cclet.2024.110810
9. [9]
  Pan Zhou , Ting Zou , Hong-Jian Song , Yu-Xiu Liu , Qing-Min Wang . Advances in organoelectrochemical copper-catalyzed reactions. Chinese Chemical Letters, 2026, 37(1): 111673-. doi: 10.1016/j.cclet.2025.111673
10. [10]
  Yuwei Liang , Jianwei Huang , Zhiqiang Zhang , Qinghong Yang , Aiwen Lei , Hong Yi . Electrochemical Mn-catalyzed nitrogenation of alkynes to nitriles via C≡C bonds cleavage. Chinese Chemical Letters, 2026, 37(4): 111166-. doi: 10.1016/j.cclet.2025.111166
11. [11]
  Haitao Liu , Youlin Deng , Dan Ling , Lingzhu Chen , Zhichao Jin . Asymmetric catalysis for the synthesis of planar chiral ferrocene derivatives. Chinese Chemical Letters, 2026, 37(3): 111793-. doi: 10.1016/j.cclet.2025.111793
12. [12]
  Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
13. [13]
  Xiang Li , Beibei Zhang , Zhixiang Wang , Xiangyu Chen . Organocatalyzed iodine-mediated reversible-deactivation radical polymerization via photoinduced charge transfer complex catalysis. Chinese Chemical Letters, 2025, 36(6): 110383-. doi: 10.1016/j.cclet.2024.110383
14. [14]
  Pei Xu , Tian-Zi Hao , Zhi-Tao Liu , Yi-Qin Liu , Hui-Xian Jiang , Dong Guo , Xu Zhu . Visible-light-induced dual catalysis for divergent reduction of nitro compounds with CO₂ radical anion. Chinese Chemical Letters, 2025, 36(10): 110899-. doi: 10.1016/j.cclet.2025.110899
15. [15]
  Hongping Zhao , Weiming Yuan . Merging catalytic electron donor-acceptor complex and copper catalysis: Enantioselective radical carbocyanation of alkenes. Chinese Chemical Letters, 2025, 36(10): 110894-. doi: 10.1016/j.cclet.2025.110894
16. [16]
  Yuanyuan Ping , Wangqing Kong . 光催化碳氢键官能团化合成1-苯基-1,2-乙二醇. University Chemistry, 2025, 40(6): 238-247. doi: 10.12461/PKU.DXHX202408092
17. [17]
  Xinxin Wu . 基础有机化学教学中自由基重排反应的课程设计及其课程思政元素的融入. University Chemistry, 2025, 40(6): 316-325. doi: 10.12461/PKU.DXHX202408055
18. [18]
  Jieshuai Xiao , Yuan Zheng , Yue Zhao , Zhuangzhi Shi , Minyan Wang . Asymmetric Nozaki-Hiyama-Kishi (NHK)-type reaction of isatins with aromatic iodides by cobalt catalysis. Chinese Chemical Letters, 2025, 36(5): 110243-. doi: 10.1016/j.cclet.2024.110243
19. [19]
  Pengfu Gao , Yuan Geng , Wei Gong . Homochiral metal-organic frameworks bearing privileged ligands for heterogeneous asymmetric catalysis. Chinese Journal of Structural Chemistry, 2025, 44(10): 100719-100719. doi: 10.1016/j.cjsc.2025.100719
20. [20]
  Xue Du , Ze-Hua Sun , Penglei Zhang , Li-Ping Xu , Xiaodong Xiong . Asymmetric chloro– and selenocyclization of 2-alkenyl anilides enabled by tertiary ammonium salt catalysis. Chinese Chemical Letters, 2026, 37(4): 111259-. doi: 10.1016/j.cclet.2025.111259

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(102)
HTML views(12)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142