Russian Chemical Bulletin

, Volume 49, Issue 2, pp 378–380 | Cite as

On the mechanism of titanium-catalyzed cyclopropanation of esters with aliphatic organomagnesium compounds. Deuterium distribution in the reaction products of (CD3)2CHMgBr with ethyl 3-chloropropionate in the presence of titanium tetraisopropoxide

  • O. L. Epstein
  • A. I. Savchenko
  • O. G. Kulinkovich
Brief Communications

Abstract

The reaction of (CD3)2CHMgBr with ethyl 3-chloropropionate in the presence of catalytic amounts of Ti(OPr)4 results in (E)-1-(2-chloroethyl)-3,3-dideuterio-2-trideuterio-methylcyclopropanol and (CD3)2CDH, identified by mass spectrometry. The reaction mechanism is discussed.

Key words

cyclopropanation cyclopropanols titanium alkoxides Grignard reagents esters β-elimination titanacyclopropanes 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    M. T. Reetz,Organotitanium Reagents in Organic Synthesis, Springer-Verlag, Berlin-Heidelberg, 1986.Google Scholar
  2. 2.
    F. N. Tebbe, G. W. Pazrshall, and G. S. Reddy,J. Am. Chem. Soc., 1978,100, 3611.CrossRefGoogle Scholar
  3. 3.
    S. H. Pine, R. J. Petit, G. D. Geib, S. J. Gru, C. H. Gallego, T. Tijerina, and R. D. Pine,J. Org. Chem., 1985,50, 1212; S. H. Pine,Organic Reactions, 1992,43, 1.CrossRefGoogle Scholar
  4. 4.
    J. R. Stiele and R. H. Grubbs,J. Am. Chem. Soc., 1983,105, 1664; L. Clawson, S. L. Buchwald, and R. H. Grubbs,Tetrahedron Lett., 1984,25, 5733.CrossRefGoogle Scholar
  5. 5.
    N. A. Petasis and E. I. Browej,J. Am. Chem. Soc., 1990,112, 6392.CrossRefGoogle Scholar
  6. 6.
    J. Cheon, D. M. Rogers, and G. S. Girolani,J. Am. Chem. Soc., 1997,119, 6804; J. Cheon, L. H. Dubois, and G. S. Girolani,J. Am. Chem. Soc., 1997,119, 6814.CrossRefGoogle Scholar
  7. 7.
    O. G. Kulinkovich, S. V. Sviridov, and D. A. Vasilevskii,Synthesis, 1991, 234.Google Scholar
  8. 8.
    O. G. Kulinkovich, S. V. Sviridov, D. A. Vasilevskii, and T. S. Pritytskaya,Zh. Org. Khim., 1989,25, 2244 [J. Org. Chem. USSR, 1990,25, 2027 (Engl. Transl.)]; O. G. Kulinkovich, D. A. Vasilevskii, A. I. Savchenko, and S. V. Sviridov,Zh. Org. Khim., 1991,27, 1428 [J. Org. Chem. USSR, 1992,27, 1429 (Engl. Transl.)].Google Scholar
  9. 9.
    P. J. Davidson, M. F. Lappert, and R. Pearce,Chem. Rev., 1976,76, 219; M. L. Steierwald and W. A. Goddard, III,J. Am. Chem. Soc., 1984,106, 308.CrossRefGoogle Scholar
  10. 10.
    R. R. Schrock and G. W. Parshall,Chem. Rev., 1976,76, 243; B. J. Burger, M. E. Thompson, W. D. Cotter, and J. E. Bercaw,J. Am. Chem. Soc., 1990,112, 1566.CrossRefGoogle Scholar
  11. 11.
    O. M. Nefedov, A. I. Ioffe, and L. G. Menchikov,Khimiya karbenov [Chemistry of Carbenes], Khimiya, Moscow, 1990, p. 233 (in Russian).Google Scholar
  12. 12.
    E. J. Corey, S. A. Rao, and M. C. Noe,J. Am. Chem. Soc., 1994,116, 9345; J. Lee, H. Kim, and J. K. Cha,J. Am. Chem. Soc., 1996,118, 4198.CrossRefGoogle Scholar
  13. 13.
    E. Breitmaier and W. Voelter,Carbon-13 NMR Spectroscopy: High Resolution Methods and Application in Organic Chemistry and Biochemistry, VCH, New York, 1987, 337.Google Scholar
  14. 14.
    R. F. Nystrom, W. H. Yanks, and W. G. Brown,J. Am. Chem. Soc., 1948,70, 441.CrossRefGoogle Scholar

Copyright information

© Kluwer Academic/Plenum Publishers 2000

Authors and Affiliations

  • O. L. Epstein
    • 1
  • A. I. Savchenko
    • 1
  • O. G. Kulinkovich
    • 1
  1. 1.Department of Organic ChemistryBelorussian State UniversityMinskBelarus

Personalised recommendations