The self-disproportionation of enantiomers (SDE) of α-amino acid derivatives: facets of steric and electronic properties

Takuma Hosaka, Tomomi Imai, Alicja Wzorek, Magdalena Marcinkowska, Anna Kolbus, Osamu Kitagawa, Vadim A. Soloshonok, Karel D. Klika

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

α-Amino acids (α-AAs) are in extremely high demand in nearly every sector of the food and health-related chemical industries and continue to be the subject of intense multidisciplinary research. The self-disproportionation of enantiomers (SDE) is an emerging and one of the least studied areas of α-AA or enantiomeric properties, critically important for their production and application. In the present work, we report a detailed study of the SDE via achiral, gravity-driven column chromatography for a set of N-acylated, N-carbonylated, N-fluoroacylated, and N-thioacylated α-amino acid esters. As well as thioacylation, attention was paid to the effect of altering the R group of the ester functionality, the side chain, or that of the acyl group attached to the amide nitrogen, whereby it was found that electron-withdrawing groups in the latter moiety had a pronounced effect on the magnitude and behavior of the resulting SDE phenomenon. Intriguingly, in the case of N-fluoroacylated derivatives, by favoring the formation of dimeric associates and effecting a strong bias toward homochiral associates over heterochiral associates, the SDE magnitude was greatly reduced contrary to intuitive expectations. Energy estimates resulted from DFT calculations.

Original languageEnglish
Pages (from-to)283-294
Number of pages12
JournalAmino Acids
Volume51
Issue number2
DOIs
Publication statusPublished - 2019 Feb 7

Keywords

  • Achiral column chromatography
  • DFT calculations
  • Enantioenrichment/-depletion
  • Molecular chirality
  • N-(Thio)acylated α-amino acid esters
  • Self-disproportionation of enantiomers (SDE)

ASJC Scopus subject areas

  • Biochemistry
  • Clinical Biochemistry
  • Organic Chemistry

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