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 journalArticle

2 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
JournalAmino Acids
DOIs
Publication statusAccepted/In press - 2018 Jan 1

Fingerprint

Enantiomers
Electronic properties
Derivatives
Amino Acids
Esters
Column chromatography
Chemical industry
Discrete Fourier transforms
Amides
Gravitation
Nitrogen
Health
Electrons

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

Cite this

The self-disproportionation of enantiomers (SDE) of α-amino acid derivatives : facets of steric and electronic properties. / Hosaka, Takuma; Imai, Tomomi; Wzorek, Alicja; Marcinkowska, Magdalena; Kolbus, Anna; Kitagawa, Osamu; Soloshonok, Vadim A.; Klika, Karel D.

In: Amino Acids, 01.01.2018.

Research output: Contribution to journalArticle

Hosaka, Takuma ; Imai, Tomomi ; Wzorek, Alicja ; Marcinkowska, Magdalena ; Kolbus, Anna ; Kitagawa, Osamu ; Soloshonok, Vadim A. ; Klika, Karel D. / The self-disproportionation of enantiomers (SDE) of α-amino acid derivatives : facets of steric and electronic properties. In: Amino Acids. 2018.
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