Advertisement

Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Interaction of diazoalkanes with unsaturated compounds

12. Stereochemistry of cyclopropanation of norbornenes with diazomethane in the presence of transition metal complexes

Abstract

The stereochemistry of cyclopropanation of norbornenes with diazomethane in the presence of Cu, Pd, and Rh compounds has been studied. Stereoselectivity of the cyclopropanation depends on the nature of the transition metal and does not depend on its valent state or ligand environment. The reaction proceeds predominantly asexo-cycloaddition of the methylene fragment. The greatest amount ofendo-isomer (up to 47 %) is formed in cyclopropanation of norbornadiene andexo-tricyclo[3.2.1.02,4]oct-6-ene in the presence of Cu and Rh compounds.

This is a preview of subscription content, log in to check access.

References

  1. 1.

    U. M. Dzhemilev, V. A. Dokichev, S. Z. Sultanov, S. L. Khursan, O. M. Nefedov, Yu. V. Tomilov, and A. B. Kostitsyn,Izv. Akad. Nauk, Ser. Khim. 1992, 2353 [Bull. Russ. Acad. Sci, Div. Chem. Sci., 1992 (Engl. Transl.)].

  2. 2.

    Houben-Weyl,Methoden der Organishen Chemie, Georg-Thieme Verlag, Stuttgart, 1971,IV/3.

  3. 3.

    O. M. Nefedov, A. I. Ioffe, and L. G. Menchikov,Khimiya Karbenov [Carbene Chemistry], Khimiya, Moscow, 1990, 158 (in Russian).

  4. 4.

    G. Maas,Topics Curr. Chem., 1987,137, 75.

  5. 5.

    Houben-Weyl,Methoden der Organishen Chemie, Georg-Thieme Verlag, Stuttgart, 1989,E 19b.

  6. 6.

    U. M. Dzhemilev, V. A. Dokichev, S. Z. Sultanov, R. I. Khusnutdinov, Yu. V. Tomilov, O. M. Nefedov, and G. A. Tolstikov,Izv. Akad. Nauk SSSR, Ser. Khim., 1989, 1861 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1989 (Engl. Transl.)].

  7. 7.

    O. M. Nefedov, I. E. Dolgii, Yu. V. Tomilov, and V. G. Bordakov,Izv. Akad. Nauk SSSR, Ser. Khim., 1984, 119 [Bull. Acad. Sci. USSR, Div. Chem., Sci., 1984 (Engl. Transl.)].

  8. 8.

    Yu. V. Tomilov, V. G. Bordakov, I. E. Dolgii, and O. M. Nefedov,Izv. Akad. Nauk SSSR, Ser. Khim., 1984, 582 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1984 (Engl. Transl.)].

  9. 9.

    I. V. Kazimirchik, K. A. Lukin, I. L. Tatarnyuk, G. F. Bebikh, and N. S. Zefirov,Zh. Organ. Khimii., 1958,21, 313 [J. Org. Chem. 1958 (Engl. Transl.)].

  10. 10.

    J. Haywood-Farmer, R. E. Pincook, and J. I. Wells,Tetrahedron, 1966,22, 2007.

  11. 11.

    B. Halton, M. A. Battiste, R. Rehberg, C. L. Deyrup, and M. E. Brennan,J. Am. Chem. Soc., 1967,89, 5964.

  12. 12.

    R. Bricker, H. Kessler, and G. Zimmermann,Chem. Ber., 1978,111, 3200.

  13. 13.

    I. V. Kazimirchik, K. A. Lukin,Zh. Organ. Khimii, 1985, 21, 1401 [J. Org. Chem., 1985 (Engl. Transl.)].

  14. 14.

    L. M. Halilov, O. V. Shitikova, V. S. Sultanova, V. A. Dokichev, S. Z. Sultanov, A. A. Panasenko, U. M. Dzhemilev, and G. A. Tolstikov,Izv. Akad. Nauk SSSR, Ser. Khim., 1990, 555 [Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.)].

  15. 15.

    G. Wipff, and K. Morokuma,Tetrahedron Lett., 1980,21, 7445.

  16. 16.

    A. J. Anciaux, A. J. Hubert, A. F. Noels, and N. Petiniot, Ph. Teyssie,J. Org. Chem., 1980,45, 695.

  17. 17.

    J. Kotwitz and H. Vorbruggen,Synthesis, 1975, 636.

  18. 18.

    S. C. Clarke, K. J. Frayne, and B. L. Johson,Tetrahedron, 1969,25, 1265.

Download references

Author information

Additional information

For part 11 see ref. 1.

Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 733–735, April, 1993.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Dzhemilev, U.M., Dokichev, V.A., Maidanova, I.O. et al. Interaction of diazoalkanes with unsaturated compounds. Russ Chem Bull 42, 697–700 (1993). https://doi.org/10.1007/BF00704005

Download citation

Key words

  • metallocomplex catalysis
  • catalytic cyclopropanation of olefins
  • stereochemistry
  • diazomethane
  • norbornene hydrocarbons