Synthetic Transformations of Higher Terpenoids. 38.* Synthesis of Conjugates Containing β-Carboline and Tricyclic Diterpenoids

  • M. A. Gromova
  • Yu. V. Kharitonov
  • T. V. Rybalova
  • E. E. Shul’tsEmail author

The synthesis and properties of tricyclic pimaranes containing a C-16 β-carboline are reported. A Pictet–Spengler reaction of methyl 15-oxo-16-formylisopimarate (prepared in situ from the 15-oxo-15,16-dihydroisopimarate) and tryptamine or tryptophan methyl ester in the presence of trifluoroacetic acid formed a mixture of terpenoid 1,2,3,4-tetrahydro-β-carbolines, 3,4-dihydro-β-carbolines, and β-carbolines. Tetrahydro- and dihydro-β-carbolines in CHCl3 were oxidized to the corresponding β-carbolines by treatment in air with basic Al2O3.


diterpenoids isopimaric acid β-carbolines heterocyclic compounds Pictet–Spengler reaction XSA 



The work was financially supported by RFBR Grants No. 17-43-543235 (p_mol_a) and No. 18-03-01012. Analytical and spectral studies were performed at the Khimiya Common Use Center at IOC, SB, RAS.


  1. 1.
    M. A. Gromova, Yu. V. Kharitonov, M. A. Pokrovskii, I. Yu. Bagryanskaya, A. G. Pokrovskii, and E. E. Shul’ts, Chem. Nat. Compd., 55, 52 (2019).CrossRefGoogle Scholar
  2. 2.
    N. G. Paciaroni, R. Ratnayake, J. H. Matthews, V. M. Norwood, A. C. Arnold, L. H. Dang, H. Luesch, and R. W. Huigens, Chem. Eur. J., 23, 4327 (2017).CrossRefGoogle Scholar
  3. 3.
    S. Samundeeswari, B. Chougala, M. Holiyachi, L. Shastri, M. Kulkarni, S. Dodamani, S. Jalalpur, S. Joshi, S. Dixit, V. Sunagar, and R. Hunnur, Eur. J. Med. Chem., 128, 123 (2017).CrossRefGoogle Scholar
  4. 4.
    Q. F. Weng, J. F. Huang, Y. Zeng, Y. Y. Deng, and M. Y. Hu, Molecules, 17, 3969 (2012).CrossRefGoogle Scholar
  5. 5.
    H. J. Song, Y. X. Liu, Y. X. Liu, L. Z. Wang, and Q. M. Wang, J. Agric. Food Chem., 62, 1010 (2014).CrossRefGoogle Scholar
  6. 6.
    Z.-J. Zhang, Z.-Y. Jiang, Q. Zhu, and G.-H. Zhong, J. Agric. Food Chem., 66 (37), 9598 (2018).CrossRefGoogle Scholar
  7. 7.
    A. S. N. Formagio, P. R. Santos, K. Zanoli, T. Ueda-Nakamura, L. T. D. Tonin, C. V. Nakamura, and M. H. Sarragiotto, Eur. J. Med. Chem., 44, 4695 (2009).CrossRefGoogle Scholar
  8. 8.
    P. Ashok, H. Sharma, H. Lathiya, S. Chander, and S. Murugesan, Med. Chem. Res., 24, 513 (2015).CrossRefGoogle Scholar
  9. 9.
    W. Polanski, H. Reichmann, and G. Gille, Expert Rev. Neurother., 11, 845 (2011).CrossRefGoogle Scholar
  10. 10.
    Z. Y. Chen, R. H. Cao, L. A. Yu, B. X. Shi, J. Sun, L. A. Guo, Q. Ma, W. Yi, X. A. Song, and H. C. Song, Eur. J. Med. Chem., 45, 4740 (2010).CrossRefGoogle Scholar
  11. 11.
    R. H. Cao, X. Guan, B. X. Shi, Z. Chen, Z. H. Ren, W. Peng, and H. C. Song, Eur. J. Med. Chem., 45, 2503 (2010).CrossRefGoogle Scholar
  12. 12.
    H. Chen, P. C. Gao, M. Zhang, W. Liao, and J. W. Zhang, New J. Chem., 38, 4155 (2014).CrossRefGoogle Scholar
  13. 13.
    A. Kamal, V. Srinivasulu, V. L. Nayak, M. Sathish, N. Shankaraiah, C. Bagul, N. V. S. Reddy, N. Rangaraj, and N. Nagesh, ChemMedChem, 9, 2084 (2014).CrossRefGoogle Scholar
  14. 14.
    E. D. Cox and J. M. Cook, Chem. Rev., 95 (6), 1797 (1995).CrossRefGoogle Scholar
  15. 15.
    P. Gholamzadeh, Adv. Heterocycl. Chem., 127, 153 (2019).CrossRefGoogle Scholar
  16. 16.
    M. A. Gromova, Yu. V. Kharitonov, T. V. Rybalova, and E. E. Shul’ts, Chem. Nat. Compd., 54, 293 (2018).CrossRefGoogle Scholar
  17. 17.
    Yu. V. Kharitonov, E. E. Shul’ts, and M. M. Shakirov, Chem. Nat. Compd., 49, 1067 (2014).CrossRefGoogle Scholar
  18. 18.
    G. M. Sheldrick, SADABS, Program for Area Detector Adsorption Correction, Institute for Inorganic Chemistry, University of Goettingen, Germany, 1996.Google Scholar
  19. 19.
    G. M. Sheldrick, SHELX-97 – Programs for Crystal Structure Analysis, Release 97-2, Univ. Goettingen, Germany, 1998.Google Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • M. A. Gromova
    • 1
  • Yu. V. Kharitonov
    • 1
  • T. V. Rybalova
    • 1
    • 2
  • E. E. Shul’ts
    • 1
    • 2
    Email author
  1. 1.N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian BranchRussian Academy of SciencesNovosibirskRussia
  2. 2.Novosibirsk State UniversityNovosibirskRussia

Personalised recommendations