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

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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.

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

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Notes

  1. It should be noted that, strictly speaking, the concept of pH and pK a values is limited to aqueous systems. It is not advisable to assume their equality in the polar-organic mobile phase employed for these chromatographic experiments but they may serve for rough estimations of the reagent´s affinities to the ion exchangers relative to the “more acidic” reaction products.

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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.

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Author notes

  1. Francesca Bisi

    Present address: Department of Engineering “E. Ferrari”, University of Modena and Reggio Emilia, Via Vignolese 905/A, 41125, Modena, Italy

  2. Addolorata S. Cazzato

    Present address: Department of Life Sciences, University of Modena and Reggio Emilia, Via Campi 183, 41125, Modena, Italy

  3. Michal Kohout

    Present address: Department of Organic Chemistry, Institute of Chemical Technology, Technická 5, 166 28, Prague, Czech Republic

Authors and Affiliations

  1. Department for Analytical Chemistry, University of Vienna, Währinger Straße 38, 1090, Vienna, Austria

    Stefanie Wernisch, Francesca Bisi, Addolorata S. Cazzato, Michal Kohout & Wolfgang Lindner

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  1. Stefanie Wernisch
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  2. Francesca Bisi
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  3. Addolorata S. Cazzato
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  4. Michal Kohout
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  5. Wolfgang Lindner
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Corresponding author

Correspondence to Wolfgang Lindner.

Additional information

Published in the topical collection Amino Acid Analysis with guest editor Toshimasa Toyo'oka.

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Wernisch, S., Bisi, F., Cazzato, A.S. et al. 2-Acyl-dimedones as UV-active protective agents for chiral amino acids: enantiomer separations of the derivatives on chiral anion exchangers. Anal Bioanal Chem 405, 8011–8026 (2013). https://doi.org/10.1007/s00216-013-6932-z

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  • DOI: https://doi.org/10.1007/s00216-013-6932-z

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