Citation: Long Yin, Yuxin Shi, Rong Meng, Jiapei Shan, Weiwei Sun, Weijun Yao, Xiaowei Dou, Dong Guo. Development and enantioselective synthesis of spirobiindoles via Rh-catalyzed asymmetric arylation-spirocyclization sequence[J]. Chinese Chemical Letters, ;2026, 37(3): 111258. doi: 10.1016/j.cclet.2025.111258 shu

Development and enantioselective synthesis of spirobiindoles via Rh-catalyzed asymmetric arylation-spirocyclization sequence

Long Yin ^{a, 1} ,
Yuxin Shi ^{a, 1} ,
Rong Meng ^b ,
Jiapei Shan ^a ,
Weiwei Sun ^a ,
Weijun Yao ^c ,
Xiaowei Dou ^{b, *,} ,
Dong Guo ^{a, *,}

a.
Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University, Xuzhou 221004, China
b.
Department of Chemistry, School of Science, China Pharmaceutical University, Nanjing 211198, China
c.
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China

dxw@cpu.edu.cn

guo@xzhmu.edu.cn

Received Date: 7 February 2025
Revised Date: 15 April 2025
Accepted Date: 24 April 2025
Available Online: 26 April 2025

Figures(4)

A new type of C2-symmetric chiral spirobiindole structure is developed, and excellent diastereoselectivities and enantioselectivities (>20:1 dr & >99% ee for all examples) were obtained via an asymmetric rhodium catalysis-intramolecular spirocyclization sequence. Selective synthesis of both spirobiindole enantiomers could be achieved using the same catalyst by simply switching the substrate combination.
- Spirobiindole,
- Rhodium catalysis,
- Intramolecular spirocyclization
1. [1]
  T.P.I. Saragi, T. Spehr, A. Siebert, T. Fuhrmann-Lieker, J. Salbeck, Chem. Rev. 107 (2007) 1011–1065. doi: 10.1021/cr0501341
2. [2]
  Y.K. Qu, Q. Zheng, J. Fan, L.S. Liao, Z.Q. Jiang, Acc. Mater. Res. 2 (2021) 1261–1271. doi: 10.1021/accountsmr.1c00208
3. [3]
  S.Y. Yang, J. Wang, Z. Deng, et al., Matter 7 (2024) 3390–3421. doi: 10.1016/j.matt.2024.07.017
4. [4]
  K. Zhang, S. Zuo, P. You, T. Ru, F.E. Chen, Chin. Chem. Lett. 35 (2024) 109157. doi: 10.1016/j.cclet.2023.109157
5. [5]
  L. Yu, A. Dai, W. Zhang, et al., J. Agric. Food Chem. 70 (2022) 10693–10707. doi: 10.1021/acs.jafc.2c02301
6. [6]
  V. Molteni, D. Rhodes, K. Rubins, et al., J. Med. Chem. 43 (2000) 2031–2039. doi: 10.1021/jm990600c
7. [7]
  X. Long, M. Zhang, X. Yang, J. Deng, Org. Lett. 24 (2022) 1303–1307. doi: 10.1021/acs.orglett.1c04282
8. [8]
  P.W. Xu, J.S. Yu, C. Chen, et al., ACS Catal. 9 (2019) 1820–1882. doi: 10.1021/acscatal.8b03694
9. [9]
  A. Ding, M. Meazza, H. Guo, J.W. Yang, R. Rios, Chem. Soc. Rev. 47 (2018) 5946–5996. doi: 10.1039/c6cs00825a
10. [10]
  R. Rios, Chem. Soc. Rev. 41 (2012) 1060–1074. doi: 10.1039/C1CS15156H
11. [11]
  X. Xie, W. Huang, C. Peng, B. Han, Adv. Synth. Catal. 360 (2018) 194–228. doi: 10.1002/adsc.201700927
12. [12]
  Z. Wang, C. Hui, H. Wang, Tetrahedron Chem. 12 (2024) 100095. doi: 10.1016/j.tchem.2024.100095
13. [13]
  J.H. Xie, Q.L. Zhou, Acc. Chem. Res. 41 (2008) 581–593. doi: 10.1021/ar700137z
14. [14]
  K. Ding, Z. Han, Z. Wang, Chem. Asian J. 4 (2009) 32–41. doi: 10.1002/asia.200800192
15. [15]
  Chiral spiro ligands S.F. Zhu, Q.L. Zhou, Privileged Chiral Ligands and Catalysts Wiley-VCH, Weiheim, 2011, pp. 137–170.
16. [16]
  X. Wang, Z. Han, Z. Wang, K. Ding, Acc. Chem. Res. 54 (2021) 668–684. doi: 10.1021/acs.accounts.0c00697
17. [17]
  V.B. Birman, A.L. Rheingold, K.C. Lam, Tetrahedron: Asymmetry 10 (1999) 125–131. doi: 10.1016/S0957-4166(98)00481-9
18. [18]
  J.H. Zhang, J. Liao, X. Cui, et al., Tetrahedron: Asymmetry 13 (2002) 1363–1366. doi: 10.1016/S0957-4166(02)00360-9
19. [19]
  J.H. Xie, A.G. Hu, H. Zhou, L.X. Wang, Q.L. Zhou, Chem. Commun. 5 (2002) 480–481.
20. [20]
  X.H. Huo, J.H. Xie, Q.S. Wang, Q.L. Zhou, Adv. Synth. Catal. 349 (2007) 2477–2484. doi: 10.1002/adsc.200700109
21. [21]
  R. Zhang, S. Ge, J. Sun, J. Am. Chem. Soc. 143 (2021) 12445–12449. doi: 10.1021/jacs.1c05709
22. [22]
  A.J. Argüelles, S. Sun, B.G. Budaitis, P. Nagorny, Angew. Chem. Int. Ed. 57 (2018) 5325–5329. doi: 10.1002/anie.201713304
23. [23]
  J. Huang, M. Hong, C.C. Wang, et al., J. Org. Chem. 83 (2018) 12838–12846. doi: 10.1021/acs.joc.8b01693
24. [24]
  G.Q. Chen, B.J. Liu, J.M. Huang, et al., J. Am. Chem. Soc. 140 (2018) 8064–8068. doi: 10.1021/jacs.8b03642
25. [25]
  Q. Zhou, R. Pan, H. Shan, X. Lin, Synthesis 51 (2019) 557–563. doi: 10.1055/s-0037-1610831
26. [26]
  W. Guo, Q. Liu, J. Jiang, J. Wang, Org. Lett. 22 (2020) 3110–3113. doi: 10.1021/acs.orglett.0c00858
27. [27]
  G. Sun, Z. Wang, Z. Luo, et al., J. Org. Chem. 85 (2020) 10584–10592. doi: 10.1021/acs.joc.0c01155
28. [28]
  S. Li, J.W. Zhang, X.L. Li, D.J. Cheng, B. Tan, J. Am. Chem. Soc. 138 (2016) 16561–16566. doi: 10.1021/jacs.6b11435
29. [29]
  Z. Zheng, Y. Cao, Q. Chong, et al., J. Am. Chem. Soc. 140 (2018) 10374–10381. doi: 10.1021/jacs.8b07125
30. [30]
  X. Chang, P.L. Ma, H.C. Chen, C.Y. Li, P. Wang, Angew. Chem. Int. Ed. 59 (2020) 8937–8940. doi: 10.1002/anie.202002289
31. [31]
  L. Yin, J. Xing, Y. Wang, et al., Angew. Chem. Int. Ed. 58 (2019) 2474–2478. doi: 10.1002/anie.201812266
32. [32]
  C. Peng, C. Wang, C. Wu, et al., Org. Lett. 27 (2025) 869–873. doi: 10.1021/acs.orglett.4c04612
33. [33]
  R. Dalpozzo, Chem. Soc. Rev. 44 (2015) 742–778. doi: 10.1039/C4CS00209A
34. [34]
  Y.C. Zhang, F. Jiang, F. Shi, Acc. Chem. Res. 53 (2019) 425–446. doi: 10.3390/ma12030425
35. [35]
  M.S. Tu, K.W. Chen, P. Wu, et al., Org. Chem. Front. 8 (2021) 2643–2672. doi: 10.1039/d0qo01643h
36. [36]
  H.W. Zhao, F. Jiang, S. Chen, et al., Angew. Chem. Int. Ed. 137 (2025) e202422951. doi: 10.1002/ange.202422951
37. [37]
  J.Y. Wang, J. Sun, Angew. Chem. Int. Ed. 137 (2025) e202424773. doi: 10.1002/ange.202424773
38. [38]
  Y. Huang, T. Hayashi, Chem. Rev. 122 (2022) 14346–14404. doi: 10.1021/acs.chemrev.2c00218
39. [39]
  K. Okamoto, T. Hayashi, V.H. Rawal, Chem. Commun. 32 (2009) 4815–4817. doi: 10.1039/b904624k
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2. [2]
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3. [3]
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4. [4]
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8. [8]
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15. [15]
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