Catalysis Letters

, Volume 31, Issue 2–3, pp 143–151 | Cite as

Chiral nitrogen compounds as new modifiers for the enantioselective hydrogenation of ethyl pyruvate

  • B. Minder
  • M. Schürch
  • T. Mallat
  • A. Baiker
Article

Abstract

The enantioselective hydrogenation of ethyl pyruvate to (R)- or (S)-ethyl lactate has been studied over alumina- and carbon-supported Pt-metal catalysts modified by various heterocyclic N-compounds and substituted amides. The reactions were carried out under mild conditions in acetic acid; other solvents had a detrimental effect on enantioselectivity. An enantiomeric excess (ee) of 67% and a rate acceleration by a factor of 6, compared to the unmodified catalyst, was observed with alumina-supported Pt modified by (R)-1-(1-naphthyl)ethylamine. In contrast, carbon-supported Pd, Ru and Rh were non-selective and only little active. The studies indicated that besides naphthyl or quinolyl groups, two separate phenyl groups or one phenyl group together with two amino groups can provide a suitable anchoring of the chiral modifier on the Pt surface. The nature of interaction between the modifiers and ethyl pyruvate is briefly discussed.

Keywords

enantioselective hydrogenation chiral modifier ethyl pyruvate Pt/alumina 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. [1]
    H.U. Blaser, Chem. Rev. 92 (1992) 935.Google Scholar
  2. [2]
    Y. Orito, S. Imai and S. Niwa, J. Chem. Soc. Jpn. (1979) 1118.Google Scholar
  3. [3]
    H.U. Blaser, H.P. Jalett, D.M. Monti, J.F. Reber and J.T. Wehrli, Stud. Surf. Sci. Catal. 41 (1988) 153.Google Scholar
  4. [4]
    I.M. Sutherland, A. Ibbotson, R.B. Moyes and P.B. Wells, J. Catal. 125 (1990) 77.Google Scholar
  5. [5]
    A. Baiker, DGMK Tagungsber. 9305, 119 (1992).Google Scholar
  6. [6]
    H.U. Blaser, H.P. Jalett and J. Wiehl, J. Mol. Catal. 68 (1991)215.Google Scholar
  7. [7]
    H.U. Blaser, H.P. Jalett, D.M. Monti, A. Baiker and J.T. Wehrli, Stud. Surf. Sci. Catal. 67 (1991) 147.Google Scholar
  8. [8]
    W.A.H. Vermeer, A. Fulford, P. Johnston and P.B. Wells, J. Chem. Soc. Chem. Commun. (1993) 1053.Google Scholar
  9. [9]
    G. Wang, T. Heinz, A. Pfaltz, B. Minder, T. Mallat and A. Baiker, J. Chem. Soc. Chem. Commun. (1994) 2047.Google Scholar
  10. [10]
    B. Minder, T. Mallat, A. Baiker, G. Wang, T. Heinz and A. Pfaltz, J. Catal., submitted.Google Scholar
  11. [11]
    J.T. Wehrli, A. Baiker, D.M. Monti and H.U. Blaser, J. Mol. Catal. 61 (1990) 207.Google Scholar
  12. [12]
    J.L. Margitfalvi, P. Marti, A. Baiker, L. Botz and O. Sticher, Catal. Lett. 6 (1990) 281.Google Scholar
  13. [13]
    Y. Orito, S. Imai and S. Niwa, J. Chem. Soc. Jpn. (1980) 670.Google Scholar
  14. [14]
    J.T. Wehrli, A. Baiker, D.M. Monti, H.U. Blaser and H.P. Jalett, J. Mol. Catal. 57 (1989) 245.Google Scholar
  15. [15]
    M. Garland and H.U. Blaser, J. Am. Chem. Soc. 112 (1990) 7048.Google Scholar
  16. [16]
    E.N. Jacobson, I. Marco, M.B. France, J.S. Svendsen and K.B. Sharpless, J. Am. Chem. Soc. 111 (1989)737.Google Scholar
  17. [17]
    M. Schneider, D.G. Tuff, T. Mallat, M. Wildberger and A. Baiker, J. Catal. 147 (1994) 500.Google Scholar
  18. [18]
    A.W. Frahm, in:Methoden der Organischen Chemie (Houben-Weyl), Vol. IV/1c, Part I, eds. E. Müller and O. Bayer (Thieme, Stuttgart, 1980) p. 411.Google Scholar
  19. [19]
    M. Freifelder,Practical Catalytic Hydrogenation (Wiley Interscience, New York, 1971) p. 168.Google Scholar
  20. [20]
    R. Richter and H. Ulrich, in:The Chemistry of Cyanates and their Thio Derivatives, Part 2, ed. S. Patai (Interscience, New York, 1977) p. 619.Google Scholar
  21. [21]
    J. Zabicky, ed.,The Chemistry of Amides (Interscience, New York, 1970) p. 155.Google Scholar
  22. [22]
    R.J. Knopf, J. Chem. Eng. Data 15 (1970) 196.Google Scholar
  23. [23]
    G. Bond, P.A. Meheux, A. Ibbotson and P.B. Wells, Catal. Today 10 (1991) 371.Google Scholar
  24. [24]
    R.L. Augustine, S.K. Tanielyan and L.K. Doyle, Tetrahedron Asym. 41 (1993) 1803.Google Scholar
  25. [25]
    O. Schwalm, B. Minder, J. Weber and A. Baiker, Catal. Lett. 23 (1994) 271.Google Scholar
  26. [26]
    A. Baiker, T. Mallat, B. Minder, O. Schwalm, K.E. Simons and J. Weber, in:Chiral Reactions in Heterogeneous Catalysis, eds. G. Jannes and V. Dubois (Plenum Press, New York, 1995), in press.Google Scholar
  27. [27]
    L. Eberson and A. Senning,Organische Chemie II (VCH, Weinheim, 1984) p. 185.Google Scholar

Copyright information

© J.C. Baltzer AG, Science Publishers 1995

Authors and Affiliations

  • B. Minder
    • 1
  • M. Schürch
    • 1
  • T. Mallat
    • 1
  • A. Baiker
    • 1
  1. 1.Department of Chemical Engineering and Industrial ChemistrySwiss Federal Institute of TechnologyZurichSwitzerland

Personalised recommendations