Citation: Yuanyuan Feng, Suqin Zha, Hanqi Zhang, Biao Gao, Guijuan Zheng, Pengfei Jin, Yingyi Chen, Guangmin Yao. Rhodauricanol A, an analgesic diterpenoid with an unprecedented 5/6/5/7 tetracyclic system featuring a unique 16-oxa-tetracyclo[11.2.1.0^1,5.0^7,13]hexadecane core from Rhododendron dauricum[J]. Chinese Chemical Letters, ;2023, 34(4): 107742. doi: 10.1016/j.cclet.2022.107742 shu

Rhodauricanol A, an analgesic diterpenoid with an unprecedented 5/6/5/7 tetracyclic system featuring a unique 16-oxa-tetracyclo[11.2.1.0^1,5.0^7,13]hexadecane core from Rhododendron dauricum

Yuanyuan Feng ^a ,
Suqin Zha ^a ,
Hanqi Zhang ^a ,
Biao Gao ^a ,
Guijuan Zheng ^a ,
Pengfei Jin ^a ,
Yingyi Chen ^a ,
Guangmin Yao ^{a, b, *,}

a.
Hubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation, School of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, China
b.
State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650201, China

gyap@mail.hust.edu.cn

Received Date: 8 May 2022
Revised Date: 7 August 2022
Accepted Date: 10 August 2022
Available Online: 14 August 2022

Figures(9)

A novel diterpenoid with an unprecedented 5/6/5/7 tetracyclic system, rhodauricanol A (1), five new grayanane-derived diterpenoids, dauricanols A−E (2−6), and five known ones (7−11) were isolated from the flowers of Rhododendron dauricum. Rhodauricanol A (1) possesses a unique 5/6/5/7 tetracyclic ring system featuring a 16-oxa-tetracyclo[11.2.1.0^1,5.0^7,13]hexadecane core. Dauricanols A−C (2−4) are the first 1,3-dioxolane conjugates of grayanane diterpenoids and 5-hydroxymethylfurfural and vanillin, respectively, and dauricanols D (5) and E (6) represent the first examples of 6-deoxy-1,5-seco-grayanane diterpenoids. Their structures were determined by spectroscopic methods, quantum chemical calculation including ¹³C NMR-DP4+ analysis and ECD calculation, and single-crystal X-ray diffraction analysis. Plausible biosynthetic pathways for 1−4 were proposed. All the isolates showed significant analgesic activities, and dauricanols B (3) and C (4) showed more potent analgesic activities than the positive control, morphine.
- Rhododendron dauricum L. (Ericaceae),
- Diterpenoids,
- Single-crystal X-ray diffraction,
- Biosynthetic pathways,
- Analgesics
1. [1]
  Y. Wang, Q. Shi, M. Dong, et al., Chem. Rev. 111 (2011) 76527709. doi: 10.1021/cr100147u
2. [2]
  Y. Li, Y. Zhu, Z. Zhang, et al., Acta Pharm. Sin. B 10 (2020) 1073–1082. doi: 10.1016/j.apsb.2019.10.013
3. [3]
  J. Zhou, Z. Zuo, J. Liu, et al., Org. Chem. Front. 7 (2020) 820828. doi: 10.1039/c9qo01538h
4. [4]
  G.J. Zheng, P.F. Jin, L. Huang, et al., Bioorg. Chem. 99 (2020) 103794. doi: 10.1016/j.bioorg.2020.103794
5. [5]
  N. Hamanaka, T. Matsumoto, Tetrahedron Lett. 13 (1972) 30873090. doi: 10.1016/S0040-4039(01)85015-2
6. [6]
  S. Gasa, N. Hamanaka, S. Matsunaga, et al., Tetrahedron Lett. 17 (1976) 553556. doi: 10.1016/S0040-4039(00)77908-1
7. [7]
  T. Kan, S. Hosokawa, S. Nara, et al., J. Org. Chem. 59 (1994) 55325534. doi: 10.1021/jo00098a009
8. [8]
  K. Yu, Z. Yang, C. Liu, et al., Angew. Chem. Int. Ed. 58 (2019) 85568560. doi: 10.1002/anie.201903349
9. [9]
  A. Turlik, Y. Chen, A.C. Scruse, et al., J. Am. Chem. Soc. 141 (2019) 80888092. doi: 10.1021/jacs.9b03751
10. [10]
  L. Kong, H. Yu, M. Deng, et al., J. Am. Chem. Soc. 144 (2022) 52685273. doi: 10.1021/jacs.2c01692
11. [11]
  J. Gao, P. Rao, K. Xu, et al., J. Am. Chem. Soc. 142 (2020) 45924597. doi: 10.1021/jacs.0c00308
12. [12]
  Y. Kawamoto, F. Karube, T. Kobayashi, et al., Org. Lett. 22 (2020) 76097612. doi: 10.1021/acs.orglett.0c02811
13. [13]
  Y. Kawamoto, F. Karube, T. Kobayashi, et al., Tetrahedron 83 (2021) 131958. doi: 10.1016/j.tet.2021.131958
14. [14]
  S. Borrelly, L.A. Paquette, J. Am. Chem. Soc. 118 (1996) 727740. doi: 10.1021/ja9533454
15. [15]
  S. Chow, C. Kress, N. Albaek, et al., Org. Lett. 13 (2011) 52865289. doi: 10.1021/ol202147r
16. [16]
  C.W. Cunningham, W.M. Elballa, S.U. Vold, Neuropharmacology 151 (2019) 195207. doi: 10.1016/j.neuropharm.2019.03.006
17. [17]
  P. Jin, G. Zheng, X. Yuan, et al., Bioorg. Chem. 111 (2021) 104870. doi: 10.1016/j.bioorg.2021.104870
18. [18]
  D. Xin, P.J. Jones, N.C. Gonnella, J. Org. Chem. 83 (2018) 5035‒5043. doi: 10.1021/acs.joc.8b00338
19. [19]
  N. Grimblat, M.M. Zanardi, A.M. Sarotti, J. Org. Chem. 80 (2015) 12526‒12534. doi: 10.1021/acs.joc.5b02396
20. [20]
  S.G. Smith, J.M. Goodman, J. Am. Chem. Soc. 132 (2010) 129460112959.
21. [21]
  R. Guo, T. Lv, F. Han, et al., Chin. Chem. Lett. 31 (2020) 12541258. doi: 10.1016/j.cclet.2019.09.042
22. [22]
  J. Gao, X. Zhang, K. Shang, et al., Chin. Chem. Lett. 31 (2020) 427‒430. doi: 10.1016/j.cclet.2019.09.020
23. [23]
  J. Zhou, J. Liu, T. Dang, et al., Org. Lett. 20 (2018) 20632066. doi: 10.1021/acs.orglett.8b00606
24. [24]
  M. Jiang, Z. Wu, Q. Wu, et al., Chin. Chem. Lett. 32 (2021) 18931896. doi: 10.1016/j.cclet.2021.01.027
25. [25]
  S. Parsons, H.D. Flack, T. Wagner, Acta Crystallogr. B 69 (2013) 249259. doi: 10.1107/S2052519213010014
26. [26]
  S.F. El-Naggar, R.W. Doskotch, T.M. Odell, et al., J. Nat. Prod. 43 (1980) 617631. doi: 10.1021/np50011a016
27. [27]
  M. Zhang, Y. Zhu, G. Zhan, et al., Org. Lett. 15 (2013) 30943097. doi: 10.1021/ol401292y
28. [28]
  M. Katai, T. Terai, J. Katakawa, Mem. Osaka Inst. Technol., Ser. A 51 (2006) 16.
29. [29]
  H. Zhang, H. Wang, L. Wang, et al., J. Asian Nat. Prod. Res. 7 (2005) 8790. doi: 10.1080/10286020310001609001
30. [30]
  J.W. Burke, R.W. Doskotch, J. Nat. Prod. 53 (1990) 131137. doi: 10.1021/np50067a017
31. [31]
  J. Wang, C.P. Zhang, P.K. Ouyang, Chem. Ind. Eng. Prog. 27 (2008) 702707.
32. [32]
  H.S. Kang, J.H. Choi, W.K. Cho, et al., Arch. Pharm. Res. 27 (2004) 742750. doi: 10.1007/BF02980143
33. [33]
  R. Mogana, K. Teng-Jin, C. Wiart, et al., Biomed. Res. Int. 2014 (2014) 903529.
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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

Rhodauricanol A, an analgesic diterpenoid with an unprecedented 5/6/5/7 tetracyclic system featuring a unique 16-oxa-tetracyclo[11.2.1.01,5.07,13]hexadecane core from Rhododendron dauricum

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通讯作者: 陈斌, bchen63@163.com

Rhodauricanol A, an analgesic diterpenoid with an unprecedented 5/6/5/7 tetracyclic system featuring a unique 16-oxa-tetracyclo[11.2.1.0^1,5.0^7,13]hexadecane core from Rhododendron dauricum