Russian Journal of Organic Chemistry

, Volume 39, Issue 10, pp 1398–1405 | Cite as

Amino Alcohols with Bicyclic Carbon Skeleton. Alternative Functionalization of Nucleophilic Reaction Centers

  • L. I. Kas'yan
  • E. A. Golodaeva
  • A. O. Kas'yan
  • A. K. Isaev
Article

Abstract

Electron density distribution in the molecules of stereoisomeric N-[2-(4-nitrophenyl)-2-hydroxyethyl](bicyclo[2.2.1]hept-2-en-5-ylmethyl)amines was studied by quantum-chemical methods, and their chemical transformations were examined. According to the results of PM3 semiempirical calculations, the nitrogen atom in the amino alcohols possesses greater proton affinity, as compared to the oxygen atom. Chemoselective functionalization of the amino alcohols at the nitrogen and oxygen nucleophilic centers was effected using 4-nitrobenzoyl chloride, 4-toluenesulfonyl isocyanate, and hexamethyldisilazane in the presence of chlorotrimethylsilane. N,O-Bis-acylated amino alcohols were synthesized, one of which was subjected to oxidation with peroxyphthalic acid. The oxidation was not accompanied by heterocyclization, and it led to formation of the corresponding exo-epoxynorbornane derivative with the endo-oriented substituent at the bicyclic framework. The structure of the products was confirmed by the IR and 1H NMR spectra.

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REFERENCES

  1. 1.
    Bergmeier, S.C., Tetrahedron, 2000, vol. 56, p. 2561; Karpf, M. and Trussardi, R., J. Org. Chem., 2001, vol. 66, p. 2044; Inaba, T., Yamada, Y., Abe, H., Sagawa, S., and Cho, H., J. Org. Chem., 2000, vol. 65, p. 1623.Google Scholar
  2. 2.
    Sayer, J.M., Chadha, A., Agarwal, S.K., Yeh, H.J.C., Yagi, H., and Jerina, D.M., J. Org. Chem., 1991, vol. 56, p. 20; Bazandi, K., Zaugi, R., and Blum, J., J. Heterocycl. Chem., 1996, vol. 33, p. 1703; Abu-Shqara, E. and Blum, J., J. Heterocycl. Chem., 1990, vol. 27, p. 1197; Lee, Y.T. and Fisher, J.F., J. Org. Chem., 1993, vol. 58, p. 3712.Google Scholar
  3. 3.
    Mashkovskii, M.D., Lekarstvennye sredstva (Drugs), Moscow: Novaya Volna, 2002, vols. 1, 2.Google Scholar
  4. 4.
    Kas'yan, L.I., Kas'yan, A.O., and Tarabara, I.N., Russ. J. Org. Chem., 2001, vol. 37, p. 1361.Google Scholar
  5. 5.
    Kas'yan, A.O., Golodaeva, E.A., Tsygankov, A.V., and Kas'yan, L.I., Russ. J. Org. Chem., 2002, vol. 38, p. 1606.Google Scholar
  6. 6.
    Kas'yan, L.I., Kas'yan, A.O., and Golodaeva, E.A., Russ. J. Org. Chem., 2000, vol. 36, p. 1722.Google Scholar
  7. 7.
    Kas'yan, L.I., Golodaeva, E.A., Nadtoka, M.I., and Kas'yan, A.O., Visn. Dnipropetr. Univ., Khim., 2002, no. 8, p. 41.Google Scholar
  8. 8.
    Kas'yan, L.I., Batog, A.E., Kas'yan, A.O., Gaponova, R.G., Savel'eva, O.V., and Golodaeva, E.A., Vopr. Khim. Khim. Tekhnol., 2000, no. 1, p. 34.Google Scholar
  9. 9.
    Kas'yan, A.O., Zlenko, E.T., Golodaeva, E.A., Tarabara, I.N., and Kas'yan, L.I., Abstracts of Papers, Mezhdunarodnaya nauchnaya konferentsiya “Khimiya i tekhnologiya karkasnykh soedinenii” (Int. Scientific Conf. “Chemistry and Technology of Cage-Like Compounds”), Volgograd, 2001, p. 103.Google Scholar
  10. 10.
    Alder, K., Krieger, H., and Weiβ, H., Chem. Ber., 1955, vol. 88, p. 144; Alder, K., Heimbach, K., and Reubke, R., Chem. Ber., 1958, vol. 91, p. 1516; Wilder, P. and Knight, D.B., J. Org. Chem., 1965, vol. 30, p. 3078.Google Scholar
  11. 11.
    Dewar, M.J.S., Zoebisch, E.G., Healy, E.F., and Stewart, J.J.P., J. Am. Chem. Soc., 1985, vol. 107, p. 3902; Stewart, J.J.P., J. Comput. Chem., 1989, vol. 10, p. 209.Google Scholar
  12. 12.
    Nakanishi, K., Infrared Absorption Spectroscopy. Practical, San Francisco: Holden-Day, 1962.Google Scholar
  13. 13.
    Zefirov, N.S. and Sokolov, V.I., Usp. Khim., 1967, vol. 36, p. 243.Google Scholar
  14. 14.
    Kasyan, L.I., Sereda, S.V., Potekhin, K.A., and Kasyan, A.O., Heteroatom Chem., 1997, vol. 8, p. 177.Google Scholar
  15. 15.
    Lukevits, E.Ya., Libert, L.I., and Voronkov, M.G., Usp. Khim., 1970, vol. 29, p. 2005; Birgele, I.S., Kemme, A.A., and Kupge, E.L., Kremniiorganicheskie proizvodnye aminospirtov: fiziko-khimicheskie issledovaniya (Organosilicon Derivatives of Amino Alcohols: Physicochemical Studies), Riga: Zinatne, 1987.Google Scholar
  16. 16.
    Kasyan, L.I., Tarabara, I.N., Savel'yeva, O.A., and Kasyan, A.O., Heteroatom Chem., 2001, vol. 12, p. 119.Google Scholar
  17. 17.
    Kas'yan, L.I., Kas'yan, A.O., Gorb, L.G., and Klebanov, B.M., Russ. J. Org. Chem., 1995, vol. 31, p. 626.Google Scholar
  18. 18.
    Tori, K., Kitahonoki, K., Tanida, H., and Tsuji, T., Tetrahedron Lett., 1964, vol. 7, p. 559; Zefirov, N.S., Kasyan, L.I., Gnedenkov, L.Yu., Shashkov, A.S., and Cherepanova, E.G., Tetrahedron Lett., 1979, vol. 11, p. 949.Google Scholar
  19. 19.
    Onishchenko, A.S., Dienovyi sintez (Diels-Alder Reaction), Moscow: Akad. Nauk SSSR, 1963.Google Scholar

Copyright information

© MAIK “Nauka/Interperiodica” 2003

Authors and Affiliations

  • L. I. Kas'yan
    • 1
  • E. A. Golodaeva
    • 1
  • A. O. Kas'yan
    • 2
  • A. K. Isaev
    • 1
  1. 1.Dnepropetrovsk National UniversityDnepropetrovskUkraine
  2. 2.Institut füur organische Chemie, Rheinisch-Westfüalische technische HochschuleAachenGermany

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