Citation: Da-Qiu Cui, Quan-Xin Li, Jia-Bo Huang, Ying-Qi Zhang, Xuan Wang, Shao-Fei Ni, Long-Wu Ye, Bo Zhou. Atroposelective transformation of vinyl cations by chiral Brønsted acid catalysis[J]. Chinese Chemical Letters, ;2026, 37(6): 111738. doi: 10.1016/j.cclet.2025.111738 shu

Atroposelective transformation of vinyl cations by chiral Brønsted acid catalysis

Da-Qiu Cui ^a ,
Quan-Xin Li ^b ,
Jia-Bo Huang ^b ,
Ying-Qi Zhang ^a ,
Xuan Wang ^a ,
Shao-Fei Ni ^{b, c, *,} ,
Long-Wu Ye ^{a, d, e} ,
Bo Zhou ^{a, *,}

a.
State Key Laboratory of Physical Chemistry of Solid Surfaces and Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
b.
College of Chemistry & Chemical Engineering and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou 515063, China
c.
Chemistry and Chemical Engineering Guangdong Laboratory, Shantou 515063, China
d.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
e.
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China

sfni@stu.edu.cn

zhoubo@xmu.edu.cn

Received Date: 5 May 2025
Revised Date: 5 August 2025
Accepted Date: 17 August 2025
Available Online: 18 August 2025

Figures(6)

Over the past decades, vinyl cations have been developed as versatile synthetic intermediates in organic chemistry, that allow the construction of various C–C and C–X bonds. However, the catalytic enantioselective transformation of vinyl cations remains one of the major challenges in asymmetric catalysis, especially for the organocatalytic enantioselective reaction. Herein, we report a chiral Brønsted acid-catalyzed atroposelective reaction of vinyl cations by combining organocatalytic diyne cyclization with C(sp²)–H functionalization of diphenols. The effective chiral induction model of vinyl cations enables the streamlined synthesis of axially chiral acyclic tetrasubstituted alkenes with the simultaneous control of chemoselectivity, regioselectivity, E/Z selectivity and enantioselectivity. Further derivatizations and applications demonstrate the potential utility of constructed axially chiral skeletons in asymmetric catalysis. Computational mechanistic studies reveal the reaction mechanism and origin of selectivities. Notably, this protocol represents the first organocatalytic asymmetric intermolecular reaction of vinyl cations, as well as the first organocatalytic enantioselective diyne cyclization.
- Axial chirality,
- Chiral Brønsted acid catalysis,
- Vinyl cations
1. [1]
  M. Hanack, Angew. Chem. Int. Ed. 17 (1978) 333–341. doi: 10.1002/anie.197803331
2. [2]
  T. Okuyama, Acc. Chem. Res. 35 (2002) 12–18. doi: 10.1021/ar0100374
3. [3]
  M. Niggemann, S. Gao, Angew. Chem. Int. Ed. 57 (2018) 16942–16944. doi: 10.1002/anie.201810701
4. [4]
  X.J. Liu, Y. Xu, C. Tang, P.C. Qian, L.W. Ye, Sci. China Chem. 65 (2022) 20–30. doi: 10.1007/s11426-021-1117-2
5. [5]
  T. Jin, M. Himuro, Y. Yamamoto, J. Am. Chem. Soc. 132 (2010) 5590–5591. doi: 10.1021/ja101633x
6. [6]
  A.J. Walkinshaw, W. Xu, M.G. Suero, M.J. Gaunt, J. Am. Chem. Soc. 135 (2013) 12532–12535. doi: 10.1021/ja405972h
7. [7]
  T. Wurm, J. Bucher, S.B. Duckworth, et al., Angew. Chem. Int. Ed. 56 (2017) 3364–3368. doi: 10.1002/anie.201700057
8. [8]
  S. Popov, B. Shao, A.L. Bagdasarian, et al., Science 361 (2018) 381–387. doi: 10.1126/science.aat5440
9. [9]
  S.E. Cleary, X. Li, L.C. Yang, et al., J. Am. Chem. Soc. 141 (2019) 3558–3565. doi: 10.1021/jacs.8b12420
10. [10]
  T. Okuyama, T. Takino, T. Sueda, M. Ochiai, J. Am. Chem. Soc. 117 (1995) 3360–3367. doi: 10.1021/ja00117a006
11. [11]
  M. Kreuzahler, A. Daniels, C. Wölper, G. Haberhauer, J. Am. Chem. Soc. 141 (2019) 1337–1348. doi: 10.1021/jacs.8b11501
12. [12]
  S. Schroeder, C. Strauch, N. Gaelings, M. Niggemann, Angew. Chem. Int. Ed. 58 (2019) 5119–5123. doi: 10.1002/anie.201810916
13. [13]
  B. Wigman, W. Lee, W. Wei, K.N. Houk, H.M. Nelson, Angew. Chem. Int. Ed. 61 (2022) e202113972. doi: 10.1002/anie.202113972
14. [14]
  T. Ikeuchi, S. Inuki, S. Oishi, H. Ohno, Angew. Chem. Int. Ed. 58 (2019) 7792–7796. doi: 10.1002/anie.201903384
15. [15]
  H. Komatsu, T. Ikeuchi, H. Tsuno, et al., Angew. Chem. Int. Ed. 60 (2021) 27019–27025. doi: 10.1002/anie.202111267
16. [16]
  F.L. Hong, Z.S. Wang, D.D. Wei, et al., J. Am. Chem. Soc. 141 (2019) 16961–16970. doi: 10.1021/jacs.9b09303
17. [17]
  F.L. Hong, C.Y. Shi, P. Hong, et al., Angew. Chem. Int. Ed. 61 (2022) e202115554. doi: 10.1002/anie.202115554
18. [18]
  H.H. Chen, Y.B. Chen, J.Z. Gao, L.W. Ye, B. Zhou, Angew. Chem. Int. Ed. 63 (2024) e202411709. doi: 10.1002/anie.202411709
19. [19]
  Y.X. Zheng, L.G. Liu, T.Q. Hu, et al., Nat. Commun. 15 (2024) 9227. doi: 10.1038/s41467-024-53605-7
20. [20]
  F.S. Li, X.Y. Zou, T.Q. Hu, et al., Sci. Adv. 10 (2024) eadq7767. doi: 10.1126/sciadv.adq7767
21. [21]
  Y.B. Chen, L.G. Liu, Z.Q. Wang, et al., Nat. Commun. 15 (2024) 2232. doi: 10.1038/s41467-024-46288-7
22. [22]
  F.L. Hong, Y.B. Chen, S.H. Ye, et al., J. Am. Chem. Soc. 142 (2020) 7618–7626. doi: 10.1021/jacs.0c01918
23. [23]
  L.J. Qi, C.T. Li, Z.Q. Huang, et al., Angew. Chem. Int. Ed. 61 (2022) e202210637. doi: 10.1002/anie.202210637
24. [24]
  C.T. Li, L.J. Qi, L.G. Liu, et al., Nat. Commun. 14 (2023) 7058. doi: 10.1038/s41467-023-42805-2
25. [25]
  Y.B. Chen, L.G. Liu, C.M. Chen, et al., Angew. Chem. Int. Ed. 62 (2023) e202303670. doi: 10.1002/anie.202303670
26. [26]
  C.Y. Weng, L.G. Liu, M. Sun, et al., Angew. Chem. Int. Ed. 64 (2025) e202418254. doi: 10.1002/anie.202418254
27. [27]
  S.K. Nistanaki, C.G. Williams, B. Wigman, et al., Science 378 (2022) 1085–1091. doi: 10.1126/science.ade5320
28. [28]
  T. Akiyama, Chem. Rev. 107 (2007) 5744–5758. doi: 10.1021/cr068374j
29. [29]
  D. Parmar, E. Sugiono, S. Raja, M. Rueping, Chem. Rev. 114 (2014) 9047–9153. doi: 10.1021/cr5001496
30. [30]
  T. James, M. van Gemmeren, B. List, Chem. Rev. 115 (2015) 9388–9409. doi: 10.1021/acs.chemrev.5b00128
31. [31]
  R. Maji, S.C. Mallojjala, S.E. Wheeler, Chem. Soc. Rev. 47 (2018) 1142–1158. doi: 10.1039/c6cs00475j
32. [32]
  J.L. Kennemur, R. Maji, M.J. Scharf, B. List, Chem. Rev. 121 (2021) 14649–14681. doi: 10.1021/acs.chemrev.1c00620
33. [33]
  T. Akiyama, J. Itoh, K. Yokota, K. Fuchibe, Angew. Chem. Int. Ed. 43 (2004) 1566–1568. doi: 10.1002/anie.200353240
34. [34]
  D. Uraguchi, M. Terada, J. Am. Chem. Soc. 126 (2004) 5356–5357. doi: 10.1021/ja0491533
35. [35]
  X.N. Wang, H.S. Yeom, L.C. Fang, et al., Acc. Chem. Res. 47 (2014) 560–578. doi: 10.1021/ar400193g
36. [36]
  G. Evano, C. Theunissen, M. Lecomte, Aldrichimica. Acta 48 (2015) 59–70.
37. [37]
  Y.B. Chen, P.C. Qian, L.W. Ye, Chem. Soc. Rev. 49 (2020) 8897–8909. doi: 10.1039/d0cs00474j
38. [38]
  F.L. Hong, L.W. Ye, Acc. Chem. Res. 53 (2020) 2003–2019. doi: 10.1021/acs.accounts.0c00417
39. [39]
  C.C. Lynch, A. Sripada, C. Wolf, Chem. Soc. Rev. 49 (2020) 8543–8583. doi: 10.1039/d0cs00769b
40. [40]
  Y.C. Hu, Y. Zhao, B. Wan, Q.A. Chen, Chem. Soc. Rev. 50 (2021) 2582–2625. doi: 10.1039/d0cs00283f
41. [41]
  L. Hu, J. Zhao, Acc. Chem. Res. 57 (2024) 855–869. doi: 10.1021/acs.accounts.3c00743
42. [42]
  B. Zhou, Y.Q. Zhang, K. Zhang, et al., Nat. Commun. 10 (2019) 3234. doi: 10.1038/s41467-019-11245-2
43. [43]
  P.F. Chen, B. Zhou, P. Wu, B. Wang, L.W. Ye, Angew. Chem. Int. Ed. 60 (2021) 27164–27170. doi: 10.1002/anie.202113464
44. [44]
  Y.Q. Zhang, Y.B. Chen, J.R. Liu, et al., Nat. Chem. 13 (2021) 1093–1100. doi: 10.1038/s41557-021-00778-z
45. [45]
  Z.S. Wang, L.J. Zhu, C.T. Li, et al., Angew. Chem. Int. Ed. 61 (2022) e202201436. doi: 10.1002/anie.202201436
46. [46]
  J. Wei, J. Zhang, J.K. Cheng, S.H. Xiang, B. Tan, Nat. Chem. 15 (2023) 647–657. doi: 10.1038/s41557-023-01179-0
47. [47]
  E. Kumarasamy, R. Raghunathan, M.P. Sibi, J. Sivaguru, Chem. Rev. 115 (2015) 11239–11300. doi: 10.1021/acs.chemrev.5b00136
48. [48]
  J.K. Cheng, S.H. Xiang, S. Li, L. Ye, B. Tan, Chem. Rev. 121 (2021) 4805–4902. doi: 10.1021/acs.chemrev.0c01306
49. [49]
  J.A. Carmona, C. Rodríguez-Franco, R. Fernández, V. Hornillos, J.M. Lassaletta, Chem. Soc. Rev. 50 (2021) 2968–2983. doi: 10.1039/d0cs00870b
50. [50]
  G. Centonze, C. Portolani, P. Righi, G. Bencivenni, Angew. Chem. Int. Ed. 62 (2023) e202303966. doi: 10.1002/anie.202303966
51. [51]
  S.H. Xiang, W.Y. Ding, Y.B. Wang, B. Tan, Nat. Catal. 7 (2024) 483–498. doi: 10.1038/s41929-024-01138-z
52. [52]
  T.A. Schmidt, V. Hutskalova, C. Sparr, Nat. Rev. Chem. 8 (2024) 497–517. doi: 10.1038/s41570-024-00618-x
53. [53]
  A.G. Woldegiorgis, X. Lin, Beilstein J. Org. Chem. 17 (2021) 2729–2764. doi: 10.3762/bjoc.17.185
54. [54]
  J.K. Cheng, B. Tan, Chem. Rec. 23 (2023) e202300147. doi: 10.1002/tcr.202300147
55. [55]
  Q.L. Zhou, Privileged Chiral Ligands and Catalysts, Wiley-VCH, Weinheim Germany, 2011.
56. [56]
  G. Bringmann, T. Gulder, T.A.M. Gulder, M. Breuning, Chem. Rev. 111 (2011) 563–639. doi: 10.1021/cr100155e
57. [57]
  X. Zhang, J. Yin, J. Yoon, Chem. Rev. 114 (2014) 4918–4959. doi: 10.1021/cr400568b
58. [58]
  J.E. Smyth, N.M. Butler, P.A. Keller, Nat. Prod. Rep. 32 (2015) 1562–1583. doi: 10.1039/C4NP00121D
59. [59]
  M. Basilaia, M.H. Chen, J. Secka, J.L. Gustafson, Acc. Chem. Res. 55 (2022) 2904–2919. doi: 10.1021/acs.accounts.2c00500
60. [60]
  J. Feng, Z. Gu, SynOpen (2021) 68–85 05.
61. [61]
  S. Wu, S.H. Xiang, J.K. Cheng, B. Tan, Tetrahedron Chem. 1 (2022) 100009. doi: 10.1016/j.tchem.2022.100009
62. [62]
  P.F. Qian, T. Zhou, B.F. Shi, Chem. Commun. 59 (2023) 12669–12684. doi: 10.1039/d3cc03592a
63. [63]
  J.Y. Zou, W.Y. Xu, J. Wang, Q. Liu, Y. He, Synthesis 56 (2024) 1862–1872. doi: 10.1055/a-2230-0759
64. [64]
  Y. Tan, S. Jia, F. Hu, et al., J. Am. Chem. Soc. 140 (2018) 16893–16898. doi: 10.1021/jacs.8b09893
65. [65]
  C. Ma, F.T. Sheng, H.Q. Wang, et al., J. Am. Chem. Soc. 142 (2020) 15686–15696. doi: 10.1021/jacs.0c00208
66. [66]
  L. Jin, Q.J. Yao, P.P. Xie, et al., Chem 6 (2020) 497–511.
67. [67]
  D. Yokose, Y. Nagashima, S. Kinoshita, J. Nogami, K. Tanaka, Angew. Chem. Int. Ed. 61 (2022) e202202542. doi: 10.1002/anie.202202542
68. [68]
  W. Li, S. Chen, J. Xie, et al., Nat. Synth. 2 (2023) 140–151.
69. [69]
  J. Wang, J. Gu, J.Y. Zou, et al., Nat. Commun. 15 (2024) 3254. doi: 10.3390/polym16233254
70. [70]
  P. Hu, L. Hu, X.X. Li, et al., Angew. Chem. Int. Ed. 63 (2024) e202312923. doi: 10.1002/anie.202312923
71. [71]
  Q.-H. Wu, M. Duan, Y. Chen, et al., Nat. Catal. 7 (2024) 185–194. doi: 10.1038/s41929-023-01097-x
72. [72]
  F. Wu, Y. Zhang, R. Zhu, Y. Huang, Nat. Chem. 16 (2024) 132–139. doi: 10.1038/s41557-023-01358-z
73. [73]
  Y.H. Miao, Z.X. Zhang, X.Y. Huang, et al., Chin. Chem. Lett. 35 (2024) 108830.
1. [1]
  Fuxing Yang , Mengjie Gong , Yifei Zhang , Bangchi Wei , Nan Huang , Jun Jiang . Organocatalytic enantioselective construction of axially chiral phosphorodithiolated styrenes. Chinese Chemical Letters, 2026, 37(1): 111219-. doi: 10.1016/j.cclet.2025.111219
2. [2]
  Deng Pan , Chuan He , Genping Huang . Mechanism and origins of enantioselectivity of iridium-catalyzed atroposelective intermolecular C(sp²)-H silylation: A ligand-enabled axial chirality transfer strategy. Chinese Chemical Letters, 2026, 37(4): 111217-. doi: 10.1016/j.cclet.2025.111217
3. [3]
  Long Jin , Jian Han , Dongmei Fang , Min Wang , Jian Liao . Pd-catalyzed asymmetric carbonyl alkynylation: Synthesis of axial chiral ynones. Chinese Chemical Letters, 2024, 35(6): 109212-. doi: 10.1016/j.cclet.2023.109212
4. [4]
  Jiajun Lu , Zhehui Liao , Tongxiang Cao , Shifa Zhu . Synergistic Brønsted/Lewis acid catalyzed atroposelective synthesis of aryl-β-naphthol. Chinese Chemical Letters, 2025, 36(1): 109842-. doi: 10.1016/j.cclet.2024.109842
5. [5]
  Wentao Xu , Fuqin Zheng , Wei Chen . Localized acidic microenvironment by Brønsted acid oxides eliminates ultrapure water requirement in PEM electrolysers. Chinese Journal of Structural Chemistry, 2025, 44(10): 100680-100680. doi: 10.1016/j.cjsc.2025.100680
6. [6]
  Runze Liu , Yankai Bian , Weili Dai . Qualitative and quantitative analysis of Brønsted and Lewis acid sites in zeolites: A combined probe-assisted 1H MAS NMR and NH3-TPD investigation. Chinese Journal of Structural Chemistry, 2024, 43(4): 100250-100250. doi: 10.1016/j.cjsc.2024.100250
7. [7]
  Zhen-Qi Wang , Lin-Wen Wei , Zhao-Qing Wang , Yan-Jie Yang , Yu Zhao , Song Liu , Yuan Huang . Modular synthesis of polyfunctionalized axial-chiral 2-arylpyridines via cobalt-catalyzed asymmetric [2 + 2 + 2] cycloaddition of diynes and nitriles. Chinese Chemical Letters, 2026, 37(4): 111377-. doi: 10.1016/j.cclet.2025.111377
8. [8]
  Qianyun Ye , Yuanyuan Liang , Yuhe Yuan , Xiaohuan Sun , Liqi Zhu , Xuan Wu , Jie Han , Rong Guo . pH-responsive chiral supramolecular cysteine-Zn²⁺-indocyanine green assemblies for triple-level chirality-specific anti-tumor efficacy. Chinese Chemical Letters, 2025, 36(5): 110432-. doi: 10.1016/j.cclet.2024.110432
9. [9]
  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
10. [10]
  Yiming Yang , Lichao Sun , Qingfeng Zhang . Plasmonic nanocrystals with intrinsic chirality: Biomolecule-directed synthesis and applications. Chinese Journal of Structural Chemistry, 2025, 44(1): 100467-100467. doi: 10.1016/j.cjsc.2024.100467
11. [11]
  Fengying Ye , Ming Hu , Jun Luo , Wei Yu , Zhirong Xu , Jinjin Fu , Yansong Zheng . Significantly boosting circularly polarized luminescence by synergy of helical and planar chirality. Chinese Chemical Letters, 2025, 36(5): 110724-. doi: 10.1016/j.cclet.2024.110724
12. [12]
  Yue Pan , Jing Ren , Yifan Sun , Luying Lu , Jia Gao , Liping Chen , Shancheng Yan , Zhiyang Li . Harnessing chirality: A new dawn in inorganic nanomaterial synthesis and biomedical applications. Chinese Chemical Letters, 2026, 37(4): 110791-. doi: 10.1016/j.cclet.2024.110791
13. [13]
  Xue-Lu Ma , Jun-Bo Lu , Yuan Zhang , Ya-Fei Jiang , Jun Li . Dinitrogen fixation on transition metal complexes with flexible axial bonding. Chinese Journal of Structural Chemistry, 2026, 45(3): 100831-100831. doi: 10.1016/j.cjsc.2025.100831
14. [14]
  Cong-Bin Ji , Ding-Xiong Xie , Mei Chen , Ye-Ying Lan , Bao-Hua Zhang , Ji-Ying Yang , Zheng-Hui Kang , Shu-Jie Chen , Yu-Wei Zhang , Yun-Lin Liu . Green synthesis of 2-trifluoromethylquinoline skeletons via organocatalytic N-[(α-trifluoromethyl)vinyl]isatins CN bond activation. Chinese Chemical Letters, 2025, 36(7): 110598-. doi: 10.1016/j.cclet.2024.110598
15. [15]
  Tianzhu Qin , Weiwei Zi . Palladium-catalyzed enantioselective [2σ + 2π] cycloadditions of vinyl-carbonyl-bicyclo[1.1.0]butanes with arylidenemalononitriles. Chinese Chemical Letters, 2026, 37(1): 111072-. doi: 10.1016/j.cclet.2025.111072
16. [16]
  Jinchen Li , Tangxin Xiao , Kai Diao , Zhouyu Wang , Leyong Wang . Supramolecular catalysis enabled by chiral molecular cages with anion-π interaction capability. Chinese Chemical Letters, 2026, 37(1): 111796-. doi: 10.1016/j.cclet.2025.111796
17. [17]
  Wei Zhou , Xi Chen , Lin Lu , Xian-Rong Song , Mu-Jia Luo , Qiang Xiao . Recent advances in electrocatalytic generation of indole-derived radical cations and their applications in organic synthesis. Chinese Chemical Letters, 2024, 35(4): 108902-. doi: 10.1016/j.cclet.2023.108902
18. [18]
  Yaru Geng , Ruiqing Li , Tingting Zhu , Xinling Li , Qianwen Guan , Huang Ye , Peng Wang , Junlin Li , Junhua Luo . Formamidine intercalation to broaden photoresponsive range in alternating-cations-interlayered hybrid perovskite. Chinese Chemical Letters, 2025, 36(8): 110216-. doi: 10.1016/j.cclet.2024.110216
19. [19]
  Xiaoqian Wang , Yanling Shen , Long Chen , Lizhi Fang , Kuppusamy Kanagaraj , Ming Rao , Chunying Fan , Wanhua Wu , Cheng Yang . Azobenzene-winged phenanthroline for supramolecular chirality sensing and multidimensional chiroptical manipulation via solvent, light, temperature, and redox. Chinese Chemical Letters, 2026, 37(2): 111710-. doi: 10.1016/j.cclet.2025.111710
20. [20]
  Yanan Zhou , Li Sheng , Lanlan Chen , Wenhua Zhang , Jinlong Yang . Axial coordinated iron-nitrogen-carbon as efficient electrocatalysts for hydrogen evolution and oxygen redox reactions. Chinese Chemical Letters, 2025, 36(1): 109588-. doi: 10.1016/j.cclet.2024.109588

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(17)
HTML views(2)

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