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Analytical and Bioanalytical Chemistry

, Volume 405, Issue 25, pp 8011–8026 | Cite as

2-Acyl-dimedones as UV-active protective agents for chiral amino acids: enantiomer separations of the derivatives on chiral anion exchangers

  • Stefanie Wernisch
  • Francesca Bisi
  • Addolorata S. Cazzato
  • Michal Kohout
  • Wolfgang LindnerEmail author
Research Paper
Part of the following topical collections:
  1. Amino Acid Analysis

Abstract

2-Acetyldimedone and 12 related compounds were employed as UV-active pre-column derivatizing agents for amino acids. Direct enantioseparation of the products was achieved using chiral anion exchanger stationary phases in polar-organic mobile phase mode. Under basic conditions, the reagents´ cyclic β-tricarbonyl motifs can give rise to exo- and endocyclic enols through tautomerization. However, with primary amines (proteinogenic and unusual amino acids, aminosulfonic and aminophosphonic acids), we exclusively observed the formation of exocyclic enamine-type products. Reaction yields depended strongly on the 2-acyl modification of the reagent; in particular, we observed a significant decrease when electronegative or sterically demanding substituents were present in α-position to the exocyclic carbonyl group. In addition to improving UV detectability of the products, the introduction of this protective group facilitated successful enantiomer separations of the amino acid derivatives on Cinchona-based chiral anion exchangers. Particularly high enantiomer selectivity was observed in combination with stationary phases bearing a new variation of selectors with π-acidic (electron-poor) bis(trifluoromethyl)phenyl groups. No racemization of the analytes occurred at any stage of the analytical method including the deprotection, which was achieved with hydrazine.

Figure

Enantiomer separation of 2-undecenoyldimedone derivatives of proteinogenic amino acids phenylalanine and tryptophan on a chiral stationary phase with anion-exchange characteristics

Keywords

Amino acids/peptides Chiral analysis HPLC Ion chromatography/ion exchange UV/VIS 

Notes

Acknowledgments

St. W. gratefully acknowledges funding from the interdisciplinary PhD program “IK Functional Molecules” of the University of Vienna. The authors thank Peter Frühauf for column packing and Roland Reischl for mass spectrometric experiments.

Supplementary material

216_2013_6932_MOESM1_ESM.pdf (268 kb)
ESM 1 (PDF 267 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Stefanie Wernisch
    • 1
  • Francesca Bisi
    • 1
    • 2
  • Addolorata S. Cazzato
    • 1
    • 3
  • Michal Kohout
    • 1
    • 4
  • Wolfgang Lindner
    • 1
    Email author
  1. 1.Department for Analytical ChemistryUniversity of ViennaViennaAustria
  2. 2.Department of Engineering “E. Ferrari”University of Modena and Reggio EmiliaModenaItaly
  3. 3.Department of Life SciencesUniversity of Modena and Reggio EmiliaModenaItaly
  4. 4.Department of Organic ChemistryInstitute of Chemical TechnologyPragueCzech Republic

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