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Synthesis of coruscanones A and B, metabolites of Piper coruscans, and related compounds

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Abstract

Base-catalyzed rearrangements of both individual 4-(acylmethylidene)butenolides and their mixtures prepared by condensation of citraconic anhydride with various phosphoranes occur successfully only in the presence of 5.2% MeONa in MeOH (molar ratio MeONa: substrate ≤ 10: 1, room temperature, 1–2 h). Under these conditions, the yields of 2-cinnamoyl-4-methylcyclopent-4-ene-1,3-dione (coruscanone B) and 2-acetyl-4-methylcyclopent-4-ene-1,3-dione are 56 and 65%, respectively. With a considerable increase in the reaction temperature or the molar ratio MeONa: substrate, formal addition of MeOH to the C(4)=C(5) double bond of these triketones becomes an appreciable (or predominant) process. A reaction of coruscanone B with CH2N2 in ether gives coruscanone A as a ~3: 2 mixture of (Z)- and (E)-methyl enolates (43%); other products (10%) result from the expansion and aromatization of the five-membered ring of the triketone. The simplest analog of coruscanone B, 2-acetyl-4-methylcyclopent-4-ene-1,3-dione, reacts with CH2N2 in a similar way.

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References

  1. X.-C. Li, D. Ferreira, M. R. Jacob, Q. Zhang, S. I. Khan, H. N. ElSohly, D.G. Nagle, T. J. Smillie, I. A. Khan, L. A. Walker, A. M. Clark, J. Am. Chem. Soc., 2004, 126, 6872.

    Article  CAS  Google Scholar 

  2. K. S. Babu, X.-C. Li, M. R. Jacob, Q. Zhang, S. I. Khan, D. Ferreira, A. M. Clark, J. Med. Chem., 2006, 49, 7877.

    Article  CAS  Google Scholar 

  3. E. I. Hwang, Y. M. Lee, S. M. Lee, W. H. Yeo, J. S. Moon, T. H. Kang, K. D. Park, S. U. Kim, Planta Med., 2007, 73, 679.

    Article  CAS  Google Scholar 

  4. H. M. Oh, S. K. Choi, J. M. Lee, S. K. Lee, H. Y. Kim, D. C. Han, H. M. Kim, K. H. Son, B. M. Kwon, Bioorg. Med. Chem., 2005, 13, 6182.

    Article  CAS  Google Scholar 

  5. S. Y. Wang, X. Y. Lan, J. H. Xiao, J. C. Yang, Y. T. Kao, S. T. Chang, Phytother. Res., 2008, 22, 213.

    Article  CAS  Google Scholar 

  6. S. Kumar, K. Jayabal, S. Y. Wang, Planta Med., 2008, 74, 956.

    Google Scholar 

  7. Y. Aoyama, T. Konoike, A. Kanda, N. Naya, M. Nakajima, Bioorg. Med. Chem. Lett., 2001, 11, 1695.

    Article  CAS  Google Scholar 

  8. O. P. Shestak, Ph.D. (Chem.) Thesis, Tikhookeansk. Inst. Bioorg. Khim. DVO RAN, Vladivostok, 1987, 210 pp. (in Russian).

  9. O. P. Shestak, V. L. Novikov, S. I. Stekhova, I. A. Gorsh-kova, Khim.-Farm. Zh., 1999, 33, 1, 18 [Pharm. Chem. J. (Engl. Transl.), 1999, 33, No. 1, 18].

    CAS  Google Scholar 

  10. O. P. Shestak, V. L. Novikov, N. G. Prokof’eva, E. L. Chaikina, Khim.-Farm. Zh., 1999, 33, 12, 5 [Pharm. Chem. J. (Engl. Transl.), 1999, 33, 631].

    Google Scholar 

  11. V. L. Novikov, O. P. Shestak, V. V. Logachev, M. M. Anisimov, Rastitel’nye resursy [Plant Resources], 2003, 39, No. 4, 87 (in Russian).

    CAS  Google Scholar 

  12. L. A. Lapshina, O. P. Shestak, A. V. Reunov, V. L. Novikov, M. M. Anisimov, Rastitel’nye resursy [Plant Resources], 2006, 44, No. 1, 107 (in Russian).

    Google Scholar 

  13. O. P. Shestak, E. A. Martyyas, M. M. Anisimov, V. L. No-vikov, Tezisy dokladov Mezhdunarodnoi nauchnoi konferentsii “Khimiya, tekhnologiya i meditsinskie aspekty prirodnykh soedinenii” (Almaty, Kazakhstan, 10–13 oktyabrya 2007 g.) [Abstrs Int. Scientific Conf. “Chemistry, Technology, and Medicinal Aspects of Natural Compounds” (Almaty, Kazakhstan, October 10–13, 2007)], Almaty, 2007, p. 250 (in Russian).

  14. L. C. Diaz, S. B. Shimokomaki, R. T. Shiota, J. Braz. Chem. Soc., 2005, 16, 482.

    Google Scholar 

  15. D. R. Gedge, G. Pattenden, J. Chem. Soc., Chem. Commun., 1978, 20, 880.

    Article  Google Scholar 

  16. N. G. Clemo, D. R. Gedge, G. Pattenden, J. Chem. Soc., Perkin Trans. 1, 1981, 5, 1448.

    Article  Google Scholar 

  17. V. A. Facundo, A. L. Sa, S. A. Silva, S. M. Morais, C. R. Matos, R. Braz-Filho, J. Braz. Chem. Soc., 2004, 15, 140.

    Article  CAS  Google Scholar 

  18. D. V. Berdyshev, V. P. Glazunov, V. L. Novikov, Tezisy dokladov VI Vserossiiskogo nauchnogo seminara “Khimiya i meditsina” (Ufa, 26–29 noyabrya 2007 g.) [Abstrs, VI All-Russia Scientific Seminar “Chemistry and Medicine” (Ufa, November 26–29, 2007)], Ufa, Gilem, 2007, P–133 (in Russian).

    Google Scholar 

  19. C. Reichardt, Losungsmittel — Effekte in der organischen Chemie, Verlag Chemie, 1969.

  20. A. K. Kiang, H. H. Lee, K. Y. Sim, J. Chem. Soc., 1962, 11, 4338.

    Article  Google Scholar 

  21. H. H. Lee, C. H. Tan, J. Chem. Soc. (C), 1967, 17, 1583.

    Google Scholar 

  22. A. A. Akhrem, A. M. Moiseenkov, F. A. Lakhvich, A. I. Poselenov, T. M. Ivanova, Izv. Akad. Nauk SSSR, Ser. Khim., 1971, 371 [Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.), 1971, 20, 305].

    Google Scholar 

  23. A. A. Akhrem, A. M. Moiseenkov, F. A. Lakhvich, A. I. Poselenov, Izv. Akad. Nauk SSSR, Ser. Khim., 1972, 143 [Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.), 1972, 21, 128].

    Google Scholar 

  24. V. L. Novikov, O. P. Shestak, N. N. Balaneva, Ya. Ya. Paulin’sh, G. B. Elyakov, Izv. Akad. Nauk Latv. SSR, Ser. Khim., 1985, 6, 718 (in Russian).

    Google Scholar 

  25. F. Ramirez, S. Dershowitz, J. Org. Chem., 1957, 22, 41.

    Article  CAS  Google Scholar 

  26. S. F. Ingham, R. A. Massy-Westropp, G. D. Reynolds, Aust. J. Chem., 1974, 27, 1477.

    CAS  Google Scholar 

  27. C. F. Ingham, R. A. Massy-Westropp, G. D. Reynolds, W. D. Thorpe, Aust. J. Chem., 1975, 28, 2499.

    Article  CAS  Google Scholar 

  28. M. Nilsson, Acta Chem. Scand., Ser. A, 1964, 18, 441.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Pacific Institute of Bioorganic Chemistry, Far-East Division of the Russian Academy of Sciences, 159 prosp. 100 Let Vladivostoku, 690022, Vladivostok, Russian Federation

    O. P. Shestak & V. L. Novikov

Authors
  1. O. P. Shestak
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  2. V. L. Novikov
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Correspondence to V. L. Novikov.

Additional information

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 82–91, January, 2010.

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Shestak, O.P., Novikov, V.L. Synthesis of coruscanones A and B, metabolites of Piper coruscans, and related compounds. Russ Chem Bull 59, 81–90 (2010). https://doi.org/10.1007/s11172-010-0048-9

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  • DOI: https://doi.org/10.1007/s11172-010-0048-9

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