Advertisement

Russian Journal of Organic Chemistry

, Volume 38, Issue 10, pp 1475–1478 | Cite as

Mechanism of Catalytic Addition of Benzeneselenol to Alkynes

  • V. P. Ananikov
  • D. A. Malyshev
  • I. P. Beletskaya
Article

Abstract

Addition of benzeneselenol to terminal alkynes HCÍÄCR, catalyzed by Pd(0) complexes, leads to formation of mixtures of mono- and bis(phenylseleno)alkenes, depending on the nature of the R substituent. Electron-donor groups (R = Bu, CH2OH, CH2NMe2) give rise to addition according to the Markownikoff rule, whereas from alkynes with electron-acceptor groups (R = Ph, COOMe) mixtures of products are formed as a result of side reactions. A probable reaction mechanism includes oxidative addition of benzeneselenol to the metal, alkyne insertion into the PdÄSe bond, and reductive elimination.

Keywords

Organic Chemistry Alkene Alkyne Reaction Mechanism Side Reaction 
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.

REFERENCES

  1. 1.
    Organoselenium Chemistry: Modern Developments in Organic Synthesis, Wirth, T., Ed., Berlin: Springer, 2000.Google Scholar
  2. 2.
    Organoselenium Chemistry: A Practical Approach, Back, T.G., Ed., New York: Oxford Univ., 1999.Google Scholar
  3. 3.
    Paulmier, C., Selenium Reagents and Intermediates in Organic Synthesis, Oxford: Pergamon, 1986.Google Scholar
  4. 4.
    The Chemistry of Organic Selenium and Tellurium Compounds, Patai, S. and Rappoport, Z., Eds., New York: Wiley, 1986, vols. 1–2.Google Scholar
  5. 5.
    Clemenson, P.I., Coord. Chem. Rev., 1990, vol. 190, pp. 171-203.Google Scholar
  6. 6.
    Lauterbach, C. and Fabian, J., Eur. J. Inorg. Chem., 1999, pp. 1995-2004 (see also references therein).Google Scholar
  7. 7.
    Kuniyasu, H., Ogawa, A., Sato, K.-I., Ryu, I., Kambe, N., and Sonoda, N., J. Am. Chem. Soc., 1992, vol. 114, pp. 5902-5903.Google Scholar
  8. 8.
    Backval, J.-E. and Ericsson, A., J. Org. Chem., 1994, vol. 59, pp. 5850-5851.Google Scholar
  9. 9.
    Kondo, T. and Mitsudo, T.-A., Chem. Rev., 2000, vol. 100, pp. 3205-3220.Google Scholar
  10. 10.
    Ogawa, A., Ikeda, T., Kimura, K., and Hirao, T., J. Am. Chem. Soc., 1999, vol. 121, pp. 5108-5114.Google Scholar
  11. 11.
    Kuniyasu, H., Ogawa, A., Sato, K.-I., Ryu, I., and Sonoda, N., Tetrahedron Lett., 1992, vol. 33, pp. 5525-5528.Google Scholar
  12. 12.
    Deryagina, E.N., Voronkov, M.G., and Korchevin, N.A., Usp. Khim., 1993, vol. 62, pp. 1173-1183.Google Scholar
  13. 13.
    Griesbaum, K., Angew. Chem., Int. Ed., 1970, vol. 9, pp. 273-287.Google Scholar
  14. 14.
    Kuniyasu, H., Ogawa, A., Miyazaki, S.-I., Ryu, I., Kambe, N., and Sonoda, N., J. Am. Chem. Soc., 1991, vol. 113, pp. 9796-9803.Google Scholar
  15. 15.
    Beletskaya, I.P. and Moberg, C., Chem. Rev., 1999, vol. 99, pp. 3435-33461.Google Scholar
  16. 16.
    Heiba, E.I. and Dessau, R.M., J. Org. Chem., 1967, vol. 32, pp. 3837-3840.Google Scholar
  17. 17.
    Back, T.G. and Krishna, M.V., J. Org. Chem., 1988, vol. 53, pp. 2533-2536.Google Scholar
  18. 18.
    Ogawa, A., Yokoyama, H., Yokoyama, K., Masawaki, T., Kambe, N., and Sonoda, N., J. Org. Chem., 1991, vol. 55, pp. 5721-5723.Google Scholar
  19. 19.
    Reich, H.J. and Cohen, M.L., J. Org. Chem., 1979, vol. 44, pp. 3148-3151.Google Scholar
  20. 20.
    Duddeck, H., Encyclopedia of Nuclear Magnetic Resonance, Grant, D.M. and Harris, R.K., Eds., Chichester: Wiley, 1996, vol. 7, pp. 4623-4636.Google Scholar
  21. 21.
    Wagner, R. and Berger, S., J. Magn. Reson. A, 1996, vol. 123, pp. 229-232.Google Scholar
  22. 22.
    Bax, A. and Freeman, R., J. Magn. Reson., 1981, vol. 44, pp. 542-561.Google Scholar
  23. 23.
    Willker, W., Leibfritz, D., Kerrsebaum, R., and Bermel, W., Magn. Reson. Chem., 1993, vol. 31, pp. 287-292.Google Scholar
  24. 24.
    Ruiz-Cabello, J., Vuister, G.W., Moonen, C.T.W., van Gelderen, P., Cohen, J.S., and van Zijl, P.C.M., J. Magn. Reson., 1992, vol. 100, pp. 282-303.Google Scholar
  25. 25.
    Braun, S., Kalinowski, H.-O., and Berger, S., 150 and More Basic NMR Experiments, Weinheim: Wiley-VCH, 1998.Google Scholar

Copyright information

© MAIK “Nauka/Interperiodica” 2002

Authors and Affiliations

  • V. P. Ananikov
    • 1
  • D. A. Malyshev
    • 1
  • I. P. Beletskaya
    • 2
  1. 1.Zelinskii Institute of Organic ChemistryRussian Academy of SciencesMoscowRussia
  2. 2.Faculty of ChemistryMoscow State UniversityVorob'evy gory, MoscowRussia

Personalised recommendations