Skip to main content
SpringerLink
Log in

Enantioselective hydrogenation of ethyl pyruvate. Influence of oxidative treatment of cinchonidine-modified platinum catalyst and hemiketal formation in alcoholic solvents

  • Published:
Catalysis Letters Aims and scope Submit manuscript

Abstract

The reasons for the increase in the rate and enantiomeric excess after oxidative (aerobic) treatment of Pt/alumina in ethanol have been investigated. It is demonstrated that this treatment results in the formation of acetic acid and consequently in the protonation of the quinuclidine n1 of cinchonidine. This favours the cinchonidine-pyruvate interaction and improves enantioselectivity. In addition, the reaction rate is enhanced due to acid catalysis of the carbonyl reduction. NMR and UV measurements indicate the rapid transformation of ethyl pyruvate to the corresponding hemiketal in primary alcohols as solvents. It is shown that the possible involvement of this hemiketal (and that formed between cinchonidine and ethyl pyruvate) as an intermediate in the pyruvate hydrogenation mechanism can be excluded.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Y. Orito, S. Imai and S. Niwa, J. Chem. Soc. Japan (1979) 1118.

  2. Y. Orito, S. Imai, S. Niwa and N.G. Hung, J. Synth. Org. Chem. Japan 37 (1979) 173.

    Google Scholar 

  3. H.U. Blaser, Chem. Rev. 92 (1992) 935.

    Google Scholar 

  4. I.M. Sutherland, A. Ibbotson, R.B. Moyes and P.B. Wells, J. Catal. 125 (1990) 77.

    Google Scholar 

  5. R.L. Augustine, S.K. Tanielyan and L.K. Doyle, Tetrahedron: Asymm. 4 (1993) 1803.

    Google Scholar 

  6. O. Schwalm, B. Minder, J. Weber and A. Baiker, Catal. Lett. 23 (1994) 271.

    Google Scholar 

  7. D.M. Monti, H.U. Blaser, H.P. Jalett, J.T. Wehrli and A. Baiker, J. Mol. Catal. 57 (1989) 245.

    Google Scholar 

  8. C. Reichardt,Solvents and Solvent Effects in Organic Chemistry (VCH, Weinheim, 1988) p. 359.

    Google Scholar 

  9. H.U. Blaser, H.P. Jalett and J. Wiehl, J. Mol. Catal. 68 (1991) 215.

    Google Scholar 

  10. P.A. Meheux, A. Ibbotson and P.B. Wells, J. Catal. 128 (1991) 387.

    Google Scholar 

  11. Y. Ogata and A. Kawasaki, in:The Chemistry of the Carbonyl Group, Vol. 2, ed. J. Zabicky (Interscience, London, 1970) p. 14.

    Google Scholar 

  12. J.E. Sarneski, H.L. Surprenant, F.K. Molen and C.N. Reilley, Anal. Chem. 47 (1975) 2116.

    Google Scholar 

  13. C.G. Moreland, A. Philip and F.I. Carroll, J. Org. Chem. 39 (1974) 2413.

    Google Scholar 

  14. S. Budavari, ed.,The Merck Index, 11th Ed. (Merck, Rahway, 1989) p. 355.

    Google Scholar 

  15. T. Mallat and A. Baiker, Catal. Today 19 (1994) 247.

    Google Scholar 

  16. J.L. Margitfalvi, B. Minder, E. Talas, L. Botz and A. Baiker, Stud. Surf. Sci. Catal. 75 (1993) 2471.

    Google Scholar 

  17. E. Tálas, L. Botz, J. Margitfalvi, O. Sticher and A. Baiker, J. Planar Chrom. 5 (1992) 28.

    Google Scholar 

  18. B. Beden, J.M. Léger and C. Lamy, in:Modern Aspects of Electrochemistry, Vol. 22, eds. J.O'M. Bockeris, B.E. Conway and R.E. White (Plenum Press, New York, 1992) p. 97.

    Google Scholar 

  19. T. Iwasita and E. Pastor, Electrochim. Acta 39 (1994) 531.

    Google Scholar 

  20. R. Parsons and T. VanderNoot, J. Electroanal. Chem. 257 (1988) 9.

    Google Scholar 

  21. U. Schröder and B. Andersson, J. Catal. 132 (1991) 402.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemical Engineering and Industrial Chemistry, Swiss Federal Institute of Technology, ETHZentrun, CH-8092, Zurich, Switzerland

    B. Minder, T. Mallat & A. Baiker

  2. Institute of Polymers, Swiss Federal Institute of Technology, ETH Zentrum, CH-8092, Zurich, Switzerland

    P. Skrabal

Authors
  1. B. Minder
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. T. Mallat
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. P. Skrabal
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. Baiker
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Minder, B., Mallat, T., Skrabal, P. et al. Enantioselective hydrogenation of ethyl pyruvate. Influence of oxidative treatment of cinchonidine-modified platinum catalyst and hemiketal formation in alcoholic solvents. Catal Lett 29, 115–124 (1994). https://doi.org/10.1007/BF00814258

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00814258

Keywords

Search

Navigation