在Pirkle型手性固定相上对NBD衍生物的手性识别研究。

A study of chiral recognition for NBD-derivatives on a Pirkle-type chiral stationary phase.

作者信息

Kato M, Fukushima T, Shimba N, Shimada I, Kawakami Y, Imai K

机构信息

Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-Ku, Tokyo 113-0033, Japan.

出版信息

Biomed Chromatogr. 2001 Jun;15(4):227-34. doi: 10.1002/bmc.47.

DOI:10.1002/bmc.47

PMID:11438962

Abstract

A chiral stationary phase (CSP 1) derived from an (S)-N-3,5-dinitrobenzoyl-1-naphthylglycine showed excellent enantiomeric separation for amino acid derivatives with a fluorogenic reagent, 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F), in high-performance liquid chromatography (HPLC). We compared elution profiles (separation factor and elution order) of NBD-amino acids and their analogs on HPLC, to determine the diastereomeric complex between the chiral moiety of CSP 1 and NBD-amino acid, which is responsible for the chiral recognition. (1)H-NMR studies of a mixture of model compound of CSP 1 and NBD-Ala suggest that the diastereomeric complex is composed of two hydrogen bonding sites at the amino proton and oxygen atom, and a pi-pi interaction by the benzofurazan structure (2,1,3-benzoxadiazole) of NBD-amino acid. Furthermore CSP 1 was able to separate esters, amides and alpha-methyl amino acids derivatized with NBD-F.

摘要

一种由（S）-N-3,5-二硝基苯甲酰基-1-萘基甘氨酸衍生而来的手性固定相（CSP 1），在高效液相色谱（HPLC）中，使用荧光试剂4-氟-7-硝基-2,1,3-苯并恶二唑（NBD-F）时，对氨基酸衍生物显示出优异的对映体分离效果。我们比较了NBD-氨基酸及其类似物在HPLC上的洗脱曲线（分离因子和洗脱顺序），以确定CSP 1的手性部分与NBD-氨基酸之间负责手性识别的非对映体复合物。CSP 1与NBD-Ala模型化合物混合物的（1）H-NMR研究表明，非对映体复合物由氨基质子和氧原子处的两个氢键位点以及NBD-氨基酸的苯并呋喃嗪结构（2,1,3-苯并恶二唑）形成的π-π相互作用组成。此外，CSP 1能够分离用NBD-F衍生化的酯、酰胺和α-甲基氨基酸。