This work presents the first study of the self-disproportionation of enantiomers via chromatography (SDEvC) of β-aminophosphonic acid esters, several of which have been synthesized for the first time. Three types of structures were examined, N-acetylated, dipeptide construction with N-Cbz glycine, and a free amine. In the latter case, this is the first time that SDEvC has been reported for free amine amino acids. In all the three types of structures, significant SDE magnitudes (Δee's up to 55%) were exhibited underscoring the ubiquitous nature of the SDE phenomenon. Chemical models of homo- versus heterochiral intermolecular interactions are proposed to rationalize the SDE magnitude differences amongst these new β-aminophosphonic acid derivatives. In addition, the incorporation of additional, competing binding modes to a molecule, was found to lead to a reduction of the SDE magnitude by shifting the intermolecular binding away from the stereogenic center and/or by leading to a convoluted binding system that disrupts the structured and relatively stable assemblies that give rise to the SDE.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1007/s00726-019-02774-7 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Structural Chemistry of C-N Axially Chiral Compounds.
J Org Chem
August 2024
Chemistry and Materials Program, College of Engineering, Shibaura Institute of Technology, 3-7-5 Toyosu, Kohto-ku, Tokyo, 135-8548, Japan.
In the last several years, atropisomers owing to the rotational restriction around a C-N single bond (C-N axially chiral compounds) have attracted significant attention in the field of synthetic organic chemistry. In particular, the highly enantioselective synthesis of various C-N axially chiral compounds and their application to asymmetric reactions have been reported by many groups. On the other hand, studies on the structural chemistry of C-N axially chiral compounds have attracted scant attention in comparison with synthetic studies.
View Article and Find Full Text PDFAltering the mobile phase composition to enhance self-disproportionation of enantiomers in achiral chromatography.
J Chromatogr A
January 2024
Department of Chemical and Process Engineering, Rzeszow University of Technology, Rzeszów, Poland. Electronic address:
The influence of mobile phase composition on the efficiency of enantiomer separation by achiral chromatography (ACh) was investigated. The separation was induced by the phenomenon of self-disproportionation of enantiomers (SDE) triggered by their homo and hetero-chiral interactions in an achiral environment. Typically, SDE occurs in apolar mobile phases of weak elution strength, which causes the separation time to extend and the process productivity to deteriorate.
View Article and Find Full Text PDFCopper (II) Ions Induced Self-Disproportionation of Enantiomers in Capillary Electrophoresis for the Quantification of Atenolol Enantiomers.
Molecules
August 2023
Henan Key Laboratory of Function-Oriented Porous Materials, College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471934, China.
Despite the fact that the self-disproportionation of enantiomers (SDE) has been found for several decades and has been widely used in crystallization, sublimation and chromatography for the purification or separation of nonracemic compounds, the phenomenon of SDE in capillary electrophoresis (CE) has never been reported up to now. Here, a new approach to separate enantiomers in CE based on SDE was demonstrated by introducing copper (II) ions into the separation media. The enantiomers of atenolol interact with copper ions to produce positively charged complexes with different electrophoretic mobilities from the single molecules.
View Article and Find Full Text PDFNatural Cannabichromene (CBC) Shows Distinct Scalemicity Grades and Enantiomeric Dominance in Strains.
J Nat Prod
April 2023
Dipartimento di Scienze del Farmaco, Largo Donegani 2, 28100 Novara, Italy.
Cannabichromene (CBC, ) occurs in Cannabis () as a scalemate having a composition that is strain-dependent in terms of both enantiomeric excess and enantiomeric dominance. In the present work, the chirality of CBC (), a noncrystalline compound, was shown not to be significantly affected by standard conditions of isolation and purification, and enantiomeric self-disproportionation effects were minimized by carrying out the chiral analysis on crude fractions rather than on purified products. A genetic basis for the different enantiomeric state of CBC in Cannabis therefore seems to exist, implying that the chirality status of natural CBC () in the plant is associated with the differential expression of CBCA-synthase isoforms and/or of associated directing proteins with antipodal enantiospecificity.
View Article and Find Full Text PDFExperimental Determination of a Chiral Ternary Solubility Diagram and Its Interpretation in Gas Antisolvent Fractionation.
Molecules
February 2023
Department of Chemical and Environmental Process Engineering, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem rkp. 3., H-1111 Budapest, Hungary.
Although crystallization has been widely applied for the enantiomeric enrichment of non-racemates both in research and in industrial applications, the physical-chemical background of chiral crystallizations is not as frequently discussed. A guide for the experimental determination of such phase equilibrium information is lacking. In the current paper, the experimental investigation of chiral melting phase equilibria, chiral solubility phase diagrams and their application in atmospheric and supercritical carbon dioxide-assisted enantiomeric enrichment is described and compared.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!