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
Article

Abstract

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.

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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

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