The self-disproportionation of enantiomers (SDE) via column chromatography of β-amino-α,α-difluorophosphonic acid derivatives

被引：12

作者：

Kwiatkowska, Magdalena ^{[1
]}

Marcinkowska, Magdalena ^{[1
]}

Wzorek, Alicja ^{[1
]}

Pajkert, Romana ^{[2
]}

Han, Jianlin ^{[3
]}

Klika, Karel D. ^{[4
]}

Soloshonok, Vadim A. ^{[5
,6
]}

Roeschenthaler, Gerd-Volker ^{[2
]}

机构：

[1] Jan Kochanowski Univ Kielce, Inst Chem, Swietokrzyska 15G, PL-25406 Kielce, Poland

[2] Jacobs Univ Bremen GGmbH, Dept Life Sci & Chem, D-28759 Bremen, Germany

[3] Nanjing Forestry Univ, Jiangsu Coinnovat Ctr Efficient Proc & Utilizat F, Coll Chem Engn, Nanjing 210037, Jiangsu, Peoples R China

[4] German Canc Res Ctr, Mol Struct Anal, Neuenheimer Feld 280, D-69120 Heidelberg, Germany

[5] Univ Basque Country UPV EHU, Dept Organ Chem 1, Fac Chem, Paseo Manuel Lardizabal 3, San Sebastian 20018, Spain

[6] Ikerbasque, Basque Fdn Sci, Maria Diaz de Haro 3,Plaza Bizkaia, Bilbao 48013, Spain

来源：

AMINO ACIDS | 2019年 / 51卷 / 09期

关键词：

Self-disproportionation of enantiomers (SDE); Achiral chromatography; Amino acids and derivatives; Molecular chirality; Enantioenrichment/-depletion; ACHIRAL-PHASE CHROMATOGRAPHY; ASYMMETRIC-SYNTHESIS; AMINOPHOSPHONIC ACIDS; ENANTIOSELECTIVE SYNTHESIS; BIOLOGICAL-ACTIVITY; PHOSPHORUS ANALOGS; SILICA-GEL; RATIONALIZATION; AMPLIFICATION; DIMENSION;

D O I：

10.1007/s00726-019-02774-7

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

This work presents the first study of the self-disproportionation of enantiomers via chromatography (SDEvC) of beta-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 (Delta ee'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 beta-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.

引用

页码：1377 / 1385

页数：9