Advertisement

Reaction of diazoalkanes with unsaturated compounds. 9 Catalyzed cyclomethylenation of trimethylsilylacetylenes by diazomethane

  • Yu. V. Tomilov
  • A. B. Kostitsyn
  • E. V. Shulishov
  • O. M. Nefedov
Organic Chemistry

Abstract

The catalyzed reaction of methyl-, propyl-, and cyclopropyltrimethylsilylacetylenes with diazomethane in the presence of CuCl leads to the corresponding cyclopropenes and bicyclobutanes with overall yields of up to 70%, and also to the products of incorporation of a methylene group into the C3-H bond of the cyclopropenes formed (2–9%). Partial catalyzed isomerization of the 1-trimethylsilyl-2-cyclopropylcyclopropene formed from trimethylsilylcyclopropylacetylene, into 1-trimethylsilyl-1-cyclopropylallene (yield ∼50%) was discovered to proceed under the reaction conditions.

Keywords

Methyl CuCl Propyl Cyclopropenes Diazomethane 
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.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Literature cited

  1. 1.
    Yu. V. Tomilov, A. B. Kostitsyn, V. A. Dokichev, et al., Izv. Akad. Nauk SSSR, Ser. Khim. No. 12, 2752 (1989).Google Scholar
  2. 2.
    Yu. V. Tomilov, A. B. Kostitsyn, and O. M. Nefedov, Izv. Akad. Nauk SSSR, Ser. Khim. No. 9, 2156 (1989).Google Scholar
  3. 3.
    G. Maas, Topics in Current Chemistry,137, 170 (1987).Google Scholar
  4. 4.
    W. von E. Doering and J. E. Coburn, Tetrahedron Lett., No. 15, 991 (1965).Google Scholar
  5. 5.
    M. Regitz and H. Heydt, 1,3-Dipolar Cycloaddition Chemistry, Vol. 1, Wiley Interscience, New York (1984), 433, 502.Google Scholar
  6. 6.
    A. T. Stell and E. Negishi, Tetrahedron Lett.,46, 5671 (1985).Google Scholar
  7. 7.
    I. E. Dolgii, G. P. Okonnishnikova, and O. M. Nefedov, Izv. Akad. Nauk SSSR, Ser. Khim., No. 4, 822 (1979).Google Scholar

Copyright information

© Plenum Publishing Corporation 1990

Authors and Affiliations

  • Yu. V. Tomilov
    • 1
  • A. B. Kostitsyn
    • 1
  • E. V. Shulishov
    • 1
  • O. M. Nefedov
    • 1
  1. 1.N. D. Zelinskii Institute of Organic ChemistryAcademy of Sciences of the USSRMoscow

Personalised recommendations