Russian Journal of Organic Chemistry

, Volume 41, Issue 6, pp 922–932 | Cite as

New Tandem Reactions of Metal Carbenoids. Intermolecular Formation of Azomethine Ylide from Methyl 2-Diazo-2-phenylacetate and Schiff Base: Intramolecular 1,3-Dipolar Cycloaddition

  • A. F. Khlebnikov
  • M. S. Novikov
  • A. A. Bespokoev
  • R. R. Kostikov
  • J. Kopf
  • Z. A. Starikova
  • M. Yu. Antipin


Rhodium acetate-catalyzed decomposition of methyl 2-diazo-2-phenylacetate in the presence of substituted N-methylbenzylideneamines possessing an activated alkenyl fragment (dipolarophile) in the side chain gives products of intramolecular cycloaddition of intermediate Z,E- and E,Z-azomethine ylides. The cycloaddition is regioselective, and the products are hexahydrochromeno[4,3-b]pyrrole derivatives. The stereoselectivity of the process depends on the temperature. In the temperature range from 20 to 80°C, the major stereoisomer is that with cis junction of the tetrahydropyran and pyrrolidine rings. N-Phenylazomethine ylides generated from methyl 2-diazo-2-phenylacetate and alkyl 4-[2-(phenyliminomethyl)phenoxy]-2-butenoates at 40°C undergo cyclization to aziridines at a higher rate, as compared to the rate of cycloaddition to the internal dipolarophile. N-Phenylazomethine ylides generated by thermolysis of the corresponding aziridine or by the “deprotonation” method react with equal regio- and stereoselectivity to give intramolecular cycloaddition products, hexahydrochromeno[4,3-b]pyrrole derivatives with trans-fused tetrahydropyran and pyrrolidine rings. Analysis of the experimental and calculation data suggests preference of the endo transition state in the cycloaddition of the examined azomethine ylides.


Pyrrole Schiff Rhodium Thermolysis Pyrrolidine 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Synthetic Application of 1,3-Dipolar Cycloaddition Chemistry toward Heterocycles and Natural Products, Padwa, A. and Pearson, W.H., Eds., New. York: Wiley, 2002.Google Scholar
  2. 2.
    Tsuge, O., Ueno, K., and Ueda, I., Heterocycles, 1981, vol. 16, p. 1503.Google Scholar
  3. 3.
    Armstrong, P., Grigg, R., Jordan, M.W., and Malone, J.F., Tetrahedron, 1985, vol. 41, p. 3547.CrossRefGoogle Scholar
  4. 4.
    Grigg, R., Donegan, G., Gunaratne, H.Q.N., Kennedy, D.A., Malone, J.F., Sridharan, V., and Thianpatanagul, S., Tetrahedron, 1989, vol. 45, p. 1723.CrossRefGoogle Scholar
  5. 5.
    Khlebnikov, A.F., Novikov, M.S., and Kostikov, R.R., Usp. Khim., 2005, vol. 74, p. 183.Google Scholar
  6. 6.
    Novikov, M.S., Khlebnikov, A.F., Besedina, O.V., and Kostikov, R.R., Tetrahedron Lett., 2001, vol. 42, p. 533.CrossRefGoogle Scholar
  7. 7.
    Voznyi, I.V., Novikov, M.S., Khlebnikov, A.F., Kostikov, R.R., and Kopf, J., J. Chem. Soc., Perkin Trans. 1, 2002, p. 1628.Google Scholar
  8. 8.
    Voznyi, I.V., Novikov, M.S., Khlebnikov, A.F., and Kostikov, R.R., Izv. Ross. Akad. Nauk, Ser. Khim., 2004, p. 1044.Google Scholar
  9. 9.
    Tsuge, O. and Kanemasa, S., Adv. Heterocycl. Chem., 1989, vol. 45, p. 231.Google Scholar
  10. 10.
    Barr, D.A., Grigg, R., Gunaratne, H.Q.N., Kemp, J., McMeekin, P., and Sridharan, V., Tetrahedron, 1988, vol. 44, p. 557.CrossRefGoogle Scholar
  11. 11.
    Kanemasa, S., Sakamoto, K., and Tsuge, O., Bull. Chem. Soc. Jpn., 1989, vol. 62, p. 1960.Google Scholar
  12. 12.
    Tsuge, O., Ueno, K., Kanemasa, S., and Yorozu, K., Bull. Chem. Soc. Jpn., 1986, vol. 59, p. 1809.Google Scholar
  13. 13.
    Achiwa, K., Sugiyama, K., and Sekiya, M., Chem. Pharm. Bull., 1985, vol. 33, p. 1975.Google Scholar
  14. 14.
    Achiwa, K. and Sekiya, M., Tetrahedron Lett., 1982, vol. 23, p. 2589.CrossRefGoogle Scholar
  15. 15.
    Burdisso, M., Gamba, A., Gandolfi, R., and Oberti, R., Tetrahedron, 1988, vol. 44, p. 3735.CrossRefGoogle Scholar
  16. 16.
    Confalone, P.N. and Huie, E.M., J. Am. Chem. Soc., 1984, vol. 106, p. 7175.CrossRefGoogle Scholar
  17. 17.
    Doyle, M.P., Wenhao, H., and Timmons, D.J., Org. Lett., 2001, vol. 3, p. 933.CrossRefPubMedGoogle Scholar

Copyright information

© MAIK “Nauka/Interperiodica” 2005

Authors and Affiliations

  • A. F. Khlebnikov
    • 1
  • M. S. Novikov
    • 1
  • A. A. Bespokoev
    • 1
  • R. R. Kostikov
    • 1
  • J. Kopf
    • 2
  • Z. A. Starikova
    • 3
  • M. Yu. Antipin
    • 3
  1. 1.St. Petersburg State UniversitySt. PetersburgRussia
  2. 2.Institut fur Anorganische ChemieHamburgGermany
  3. 3.Nesmeyanov Institute of Organometallic CompoundsRussian Academy of SciencesMoscowRussia

Personalised recommendations