Russian Journal of Organic Chemistry

, Volume 44, Issue 4, pp 516–523 | Cite as

Synthetic transformations of higher terpenoids: XVII. Intramolecular cyclization of N-furfuryl amides of the labdane series

  • Yu. V. Kharitonov
  • E. E. Shul’ts
  • M. M. Shakirov
  • G. A. Tolstikov
Article

Abstract

16-(Benzylaminomethyl)lambertianic acid methyl ester reacts with 2-methylprop-2-enoyl chloride to give unsaturated amide which readily undergoes intramolecular [4 + 2]-cycloaddition with formation of terpenoid derivatives of 10-oxa-3-azatricyclo[5.2.1.01,5]decenone. Acetylation of lambertianic acid methyl ester with acetic anhydride occurs preferentially at the 2-position of the furan ring and is accompanied by migration of the exocyclic double bond. Reductive amination of 16-acetyl-15,16-epoxylabda-8(9),13,14-triene and subsequent reaction of the resulting amine with 2-methylprop-2-enoyl chloride give intramolecular cyclization products in high yield without isolation of intermediate furfurylacryloyl derivative. Reactions of methyl 16-(benzylaminomethyl)-15,16-epoxylabda-8(9),13,14- and -8(17),13,14-trien-18-oates with maleic anhydride lead to the formation of the corresponding 10-oxa-3-azatricyclo[5.2.1.01,5]dec-8-ene-6-carboxylic acid derivatives as mixtures of diastereoisomers.

Keywords

Maleic Anhydride Intramolecular Cyclization Furan Ring Oily Substance Benzylamino 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Chernov, S.V., Shul’ts, E.E., Shakirov, M.M., and Tolstikov, G.A., Russ. J. Org. Chem., 2008, vol. 44, p. 67.Google Scholar
  2. 2.
    Jung, M.E. and Street, L.J., J. Am. Chem. Soc., 1984, vol. 106, p. 8327; Martin, S.F., Benage, B., Geraci, L.S., Hunter, J.E., and Mortimore, M., J. Am. Chem. Soc., 1991, vol. 113, p. 6161.CrossRefGoogle Scholar
  3. 3.
    Wright, D.L., Robotham, C.V., and Aboud, K., Tetrahedron Lett., 2002, vol. 43, p. 943; Ghelfi, F., Parsons, A.F., Tommasini, D., and Mucci, A., Eur. J. Org. Chem., 2001, p. 1845.CrossRefGoogle Scholar
  4. 4.
    Andres, S., Garcia-Valverde, M., Nieto, J., and Pedrosa, R., J. Org. Chem., 1999, vol. 64, p. 5230.CrossRefGoogle Scholar
  5. 5.
    Paulvannan, K., Hale, R., Mesis, R., and Chen, T., Tetrahedron Lett., 2002, vol. 43, p. 203; Fokas, D., Patterson, J.E., Slobodkin, G, and Baldino, C.M., Tetrahedron Lett., 2003, vol. 44, p. 5137.CrossRefGoogle Scholar
  6. 6.
    Lipshutz, B.H., Chem. Rev., 1986, vol. 86, p. 795; Kappe, C.O., Murphree, S.S., and Padwa, A., Tetrahedron, 1997, vol. 53, p. 14179; Zubkov, F.I., Nikitina, E.V., and Varlamov, A.V., Usp. Khim., 2005, vol. 74, p. 707.CrossRefGoogle Scholar
  7. 7.
    Kharitonov, Yu.V., Shul’ts, E.E., Shakirov, M.M., and Tolstikov, G.A., Dokl. Ross. Akad. Nauk, 2004, vol. 395, p. 122; Kharitonov, Yu.V., Shul’ts, E.E., Shakirov, M.M., and Tolstikov, G.A., Russ. J. Org. Chem., 2005, vol. 41, p. 1145.Google Scholar
  8. 8.
    Chernov, S.V., Shul’ts, E.E., Shakirov, M.M., and Tolstikov, G.A., Russ. J. Org. Chem., 2000, vol. 36, p. 1455.Google Scholar
  9. 9.
    Nazarova, Z.I., Goryaev, S.S., Simonov, A.M., and Soldatova, N.I., Khim. Geterotsikl. Soedin., 1973, p. 1011.Google Scholar
  10. 10.
    Klok, D.A., Shakirov, M.M., Grishko, V.V., and Raldugin, V.A., Izv. Ross. Akad. Nauk, Ser. Khim., 1995, p. 2514.Google Scholar
  11. 11.
    Kumpaty, H.J., Bhattacharyya, S., Rehr, E.W., and Gonzalez, A.M., Synthesis, 2003, p. 2206.Google Scholar
  12. 12.
    Neuhaus, D. and Williamson, M.P., The Nuclear Overhauser Effect in Structural and Conformational Analysis, New York: VCH, 1989.Google Scholar
  13. 13.
    Choony, N., Dadabhoy, A., and Sammes, P.G., J. Chem. Soc., Perkin Trans. 1, 1998, p. 2017.Google Scholar
  14. 14.
    Stewart, W.E. and Siddal, T.H., III, Chem. Rev., 1970, vol. 70, p. 517; Oppolzer, W., Angew. Chem. Int. Ed. Engl., 1977, vol. 16, p. 10.CrossRefGoogle Scholar

Copyright information

© MAIK Nauka 2008

Authors and Affiliations

  • Yu. V. Kharitonov
    • 1
  • E. E. Shul’ts
    • 1
  • M. M. Shakirov
    • 1
  • G. A. Tolstikov
    • 1
  1. 1.Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian DivisionRussian Academy of SciencesNovosibirskRussia

Personalised recommendations