Citation: Xuan Pan, Tao Sheng, Zhanzhu Liu. A concise total synthesis of monoterpenoid indole alkaloid (-)-voacafricine A[J]. Chinese Chemical Letters, ;2025, 36(10): 110913. doi: 10.1016/j.cclet.2025.110913 shu

A concise total synthesis of monoterpenoid indole alkaloid (-)-voacafricine A

State Key Laboratory of Bioactive Substances and Functions of Natural Medicines, Institute of Materia Medica, Peking Union Medical College and Chinese Academy of Medical Sciences, Beijing 100050, China

liuzhanzhu@imm.ac.cn

Received Date: 29 October 2024
Revised Date: 14 January 2025
Accepted Date: 3 February 2025
Available Online: 4 February 2025

Figures(9)

A concise total synthesis of novel monoterpenoid indole alkaloid (-)-voacafricine A is described, which proceeded in 14 longest linear steps and 5.2% overall yield. Key transformations comprised of (a) an organocatalytically asymmetric Pictet-Spengler cyclization/lactamization cascade reaction generating the key tetracyclic lactam skeleton; (b) asymmetric α-alkylation of carbonyl group induced by Evans' chiral auxiliary with excellent diastereoselectivity; (c) a highly efficient one-pot desulfurization/hydrogenation/debenzylation transformation using Raney Ni under hydrogen atmosphere; as well as (d) an intramolecular Vorbürggen reaction constructing the quaternary ammonium motif and the final cagelike skeleton.
- (-)-Voacafricine A,
- Pictet-Spengler cyclization,
- Evans' chiral auxiliary,
- Lawesson's reagent,
- Vorbürggen reaction
1. [1]
  C.F. Ding, H.X. Ma, J. Yang, et al., Org. Lett. 20 (2018) 2702–2706. doi: 10.1021/acs.orglett.8b00913
2. [2]
  R. Andres, Q. Wang, J.P. Zhu, Angew. Chem. Int. Ed. 62 (2023) e202301517. doi: 10.1002/anie.202301517
3. [3]
  D. Long, G.Y. Zhao, Z.Q. Liu, et al., Eur. J. Org. Chem. 2022 (2022) e202200088. doi: 10.1002/ejoc.202200088
4. [4]
  M.J. Scharf, B. List, J. Am. Chem. Soc. 144 (2022) 15451–15456. doi: 10.1021/jacs.2c06664
5. [5]
  X.W. Wang, W.J. Huang, H. Wang, B. Wu, Y.G. Zhou, Org. Lett. 24 (2022) 1727–1731. doi: 10.1021/acs.orglett.2c00368
6. [6]
  R. Andres, F.G. Sun, Q. Wang, J.P. Zhu, Angew. Chem. Int. Ed. 62 (2023) e202212831.
7. [7]
  S. Nakamura, Y. Matsuda, T. Takehara, T. Suzuki, Org. Lett. 24 (2022) 1072–1076. doi: 10.1021/acs.orglett.1c04316
8. [8]
  R. Andres, Q. Wang, J.P. Zhu, Angew. Chem. Int. Ed. 61 (2022) e202201788. doi: 10.1002/anie.202201788
9. [9]
  M. Liu, W.Z. Li, M. Huang, et al., New J. Chem. 46 (2022) 9582–9586. doi: 10.1039/d2nj00517d
10. [10]
  R. Andres, Q. Wang, J.P. Zhu, J. Am. Chem. Soc. 142 (2020) 14276–14285. doi: 10.1021/jacs.0c05804
11. [11]
  J.X. Zhu, Y.J. Lu, J. Chen, et al., RSC Adv. 10 (2020) 24251–24254. doi: 10.1039/d0ra05244b
12. [12]
  M. Retini, F. Bartoccini, G. Zappia, G. Piersanti, Eur. J. Org. Chem. 2021 (2021) 825–829. doi: 10.1002/ejoc.202001501
13. [13]
  D. Seidel, A.V. Sole, A. Adili, B. Das, M.E. Matter, Synthesis 55 (2022) 1724–1735.
14. [14]
  A. Davies, F.M. Bull, P.D. Walker, et al., Org. Lett. 22 (2020) 6349–6353. doi: 10.1021/acs.orglett.0c02190
15. [15]
  R.G. Ren, M. Li, C.M. Si, Z.Y. Mao, B.G. Wei, Tetrahedron Lett. 55 (2014) 6903–6906. doi: 10.1016/j.tetlet.2014.10.102
16. [16]
  P. Bhamboo, M. Ghosh, A. Sharma, D. Mondal, S. Bera, Tetrahedron 152 (2024) 133806. doi: 10.1016/j.tet.2023.133806
17. [17]
  L.L. Wang, Q. Yu, W. Zhang, et al., J. Am. Chem. Soc. 144 (2022) 6871–6881. doi: 10.1021/jacs.2c01133
18. [18]
  G.Y. Zhao, X.G. Xie, H.Y. Sun, et al., Org. Lett. 18 (2016) 2447–2450. doi: 10.1021/acs.orglett.6b00989
19. [19]
  P. Magnus, J.S. Mendoza, A. Stamford, M. Ladlow, P. Willis, J. Am. Chem. Soc. 114 (2002) 10232–10245.
20. [20]
  J. Stockigt, A.P. Antonchick, F. Wu, H. Waldmann, Angew. Chem. Int. Ed. 50 (2011) 8538–8564. doi: 10.1002/anie.201008071
21. [21]
  Y. Zheng, B.B. Yue, K. Wei, Y.R. Yang, J. Org. Chem. 83 (2018) 4867–4870. doi: 10.1021/acs.joc.8b00529
22. [22]
  H. Ueda, Y. Ueno, Bioorg. Med. Chem. 60 (2022) 116690–116700. doi: 10.1016/j.bmc.2022.116690
23. [23]
  R. Bereiter, E. Renard, K. Breuker, et al., J. Am. Chem. Soc. 144 (2022) 10344–10352. doi: 10.1021/jacs.2c01877
24. [24]
  F. He, Z. Sun, C. Li, et al., Org. Biomol. Chem. 21 (2023) 8273–8278. doi: 10.1039/d3ob01354e
25. [25]
  M. Roignant, J. Zhang, J. Brioche, S.R. Piettre, Eur. J. Org. Chem. 2022 (2022) e202200303.
26. [26]
  M. Pang, L.L. Shi, Y. Xie, et al., ACS Catal. 12 (2022) 5013–5021. doi: 10.1021/acscatal.2c00271
27. [27]
  Y. Sakurai, T. Yamaguchi, T. Yoshida, et al., J. Org. Chem. 88 (2022) 154–162.
28. [28]
  C. Yuan, A. Ortiz, Z. Xu, et al., J. Org. Chem. 87 (2021) 1925–1933.
29. [29]
  J. Zhang, E. Lambert, Z.F. Xu, et al., J. Org. Chem. 84 (2019) 5245–5260. doi: 10.1021/acs.joc.9b00232
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