Russian Chemical Bulletin

, Volume 54, Issue 11, pp 2562–2570 | Cite as

Reduction of substituted spiro[cyclopropane-3-(1-pyrazolines)] to spiro[cyclopropane-3-pyrazolidines] and 1-(2-aminoethyl)cyclopropylamine derivatives

  • I. V. Kostyuchenko
  • E. V. Shulishov
  • V. A. Korolev
  • V. A. Dokichev
  • Yu. V. Tomilov


Raney nickel-catalyzed hydrogenation of 5-substituted spiro[cyclopropane-3-(1-pyrazoline)]-5-carboxylates occurs with N—N bond cleavage with simultaneous cyclocondensation to give 3-aminopyrrolidin-2-ones containing a spirocyclopropane fragment. The presence of the second ester group in the pyrazoline side chain, in the position ensuring the formation of a five-membered ring results in 6,11-diazadispiro[]undecane-7,10-dione, the product of double cyclocondensation of the intermediate diamine. Hydrogenation of the aryl-substituted spiro[cyclopropane-3-(1-pyrazolines)] in the presence of acetone affords hexahydrospiro[cyclopropane-4-pyrimidines], which can be converted into the cyclopropane-containing 1,3-diamines in the individual state or as salts.

Key words

spiro[cyclopropane-3-(1-pyrazolines)] spiro[[cyclopropane-3-pyrrolidin-5-ones] hexahydrospiro[cyclopropane-4-pyrimidines] 1,3-diamines reduction cyclocondensation 


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  1. 1.
    T. L. Jacobs, Heterocyclic Compounds, Ed. R. C. Elderfield, New York, 1957, 5, 70.Google Scholar
  2. 2.
    M. R. Mish, F. M. Guerra, and E. M. Carreira, J. Am. Chem. Soc., 1997, 119, 8379.CrossRefGoogle Scholar
  3. 3.
    S. E. Denmark and J.-H. Kim, Synthesis, 1992, 229.Google Scholar
  4. 4.
    G. E. Carter, F. R. van Abeele, and J. W. Rothrock, J. Biol. Chem., 1949, 178, 325.Google Scholar
  5. 5.
    A. N. Kost, G. A. Golubeva, and R. G. Stepanov, Zh. Obshch. Khim., 1962, 32, 2240 [J. Gen. Chem. USSR, 1962, 32 (Engl. Transl.)].Google Scholar
  6. 6.
    P. Bielmeier, A. Kaiser, R. Gust, and W. Wiegrebe, Monatsh. Chem., 1996, 127, 1073.CrossRefGoogle Scholar
  7. 7.
    G. A. Whitlock and E. M. Carreira, J. Org. Chem., 1997, 62, 7916.CrossRefGoogle Scholar
  8. 8.
    S. Grabowski, J. Armbruster, and H. Prinzbach, Tetrahedron Lett., 1997, 38, 5485.CrossRefGoogle Scholar
  9. 9.
    V. A. Gorpinchenko, E. A. Yatsynich, D. V. Petrov, L. T. Karachurina, R. Yu. Khisamutdinova, N. Zh. Baschenko, V. A. Dokichev, Yu. V. Tomilov, M. S. Yunusov, and O. M. Nefedov, Khim.-Farm. Zhurn., 2005, 39, 89 [Pharm. Chem. J., 2005 (Engl. Transl.)].Google Scholar
  10. 10.
    H. Sasaki and E. M. Carreira, Synthesis, 2000, 135.Google Scholar
  11. 11.
    Yu. V. Tomilov, E. V. Shulishov, S. A. Yarygin, and O. M. Nefedov, Izv. Akad. Nauk. Ser. Khim., 1995, 2203 [Russ. Chem. Bull., 1995, 44, 2109 (Engl. Transl.)].Google Scholar
  12. 12.
    Yu. V. Tomilov, I. V. Kostyuchenko, E. V. Shulishov, and O. M. Nefedov, Izv. Akad. Nauk. Ser. Khim., 1997, 532 [Russ. Chem. Bull., 1997, 46, 511 (Engl. Transl.)].Google Scholar
  13. 13.
    Yu. V. Tomilov, I. V. Kostyuchenko, E. V. Shulishov, B. B. Averkiev, M. Yu. Antipin, and O. M. Nefedov, Izv. Akad. Nauk. Ser. Khim., 1999, 1328 [Russ. Chem. Bull., 1999, 48, 1316 (Engl. Transl.)].Google Scholar
  14. 14.
    Z. Majer, M. Kajtbr, M. Tiche, and K. Blbha, Collect. Czech. Chem. Commun., 1982, 47, 950.Google Scholar
  15. 15.
    K. D. Moeller and L. D. Rutledge, J. Org. Chem., 1992, 57, 6360.CrossRefGoogle Scholar
  16. 16.
    L. D. Rutledge, J. H. Perlman, M. C. Gershengorn, G. R. Marshal, and K. D. Moeller, J. Med. Chem., 1996, 39, 1571.CrossRefGoogle Scholar
  17. 17.
    W. Chu, J. H. Perlman, M. C. Gershengorn, and K. D. Moeller, Bioorg. Med. Chem. Lett., 1998, 8, 3093.CrossRefGoogle Scholar
  18. 18.
    J. C. Simpson, C. Ho, E. F. B. Shands, M. C. Gershengorn, G. R. Marshal, and K. D. Moeller, Bioorg. Med. Chem., 2002, 10, 291.Google Scholar
  19. 19.
    M. F. Brasa, M. Garranzo, B. Pascual-Teresa, J. Pirez-Castells, and M. R. Torres, Tetrahedron, 2002, 58, 4825.Google Scholar
  20. 20.
    R. L. Dreibelbis, H. N. Khatri, and H. M. Walborsky, J. Org. Chem., 1975, 40, 2074.CrossRefGoogle Scholar
  21. 21.
    L. Balbino, Gazz. Chim. Ital., 1889, 19, 688.Google Scholar
  22. 22.
    G. Zinner, W. Kliegel, W. Ritter, and H. Btshlke, Chem. Ber., 1966, 99, 1678.Google Scholar
  23. 23.
    E. Matter, Helv. Chim. Acta, 1947, 30, 1114.CrossRefGoogle Scholar
  24. 24.
    P. K. Jadhav and H.-W. Man, Tetrahedron. Lett., 1996, 37, 1153.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, Inc. 2005

Authors and Affiliations

  • I. V. Kostyuchenko
    • 1
  • E. V. Shulishov
    • 1
  • V. A. Korolev
    • 1
  • V. A. Dokichev
    • 2
  • Yu. V. Tomilov
    • 1
  1. 1.N. D. Zelinsky Institute of Organic ChemistryRussian Academy of SciencesMoscowRussian Federation
  2. 2.Institute of Organic Chemistry, Ufa Scientific CenterRussian Academy of SciencesUfaRussian Federation

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