Development of general chiral method for chiral branched-chain carboxylic acids

手性支链羧酸通用手性方法的发展

基本信息

批准号：
11660100
负责人：
AKASAKA Kazuaki
金额：
$ 2.3万
依托单位：
TOHOKU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2001
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11660100/
关键词：
determination of the absolute configuration ateiso fatty acide chiral fluorescent derivatization reagent chiral discrimination of methylbranched fatty acides chiral discrimination on HPLC 分岐脂肪酸絶対配置の決定蛍光不斉誘導体化キラル分離分岐脂肪酸、絶対配置の決定、

项目摘要

Methyl branched-chain fatty acids and alcohols were found in many natural products, but it had been very difficult or practically impossible to discriminate the enantiomers with very small amounts of samples. In this study, we developed general method to discriminate chiral carboxylic acids with very high sensitiovity by using a novel chiral fluorescent labeling reagent. Anteiso fatty acids having 5 to 29 carbon atoms were labelled with chiral fluorescent derivatization reagents, (1R,2R)- and (1S,2S)-2-(2,3-anthracenedicarboximido) cyclohexanol. The diastereomeric derivatives up to C20 anteiso acids were separated into two peaks on ODS column under low column temperature conditions, while those having more than C21 could not be separated by the system. The C30 column made it possible to separate diastereomeric derivatives of up to C29 anteiso acids. There was empirical rule on the elution order of diastereomeric derivatives, and it allowed us to determine the absolute configuration of the branched-chain carboxylic acids by using both enantiomers of the reagents. This method made it possible to determine absolute configurations of methyl branched fatty acids in a novel ceramide isolated from the Epiphytic Dinoflagellate Coollia monotis and glycoglycerolipid S365A isolated from Corynebacterium aquaticum, and it made also possible to determine absolute configuration at the two cyclopropane moieties of plakoside A, an immunosuppressive marine galactosphingolipid.

在许多天然产物中发现甲基支链脂肪酸和醇，但是用很少的样品区分对映异构体是非常困难或几乎不可能的。在这项研究中，我们开发了使用新型手性荧光标记试剂来区分具有非常高灵敏度的手性羧酸的通用方法。具有5至29个碳原子的反毒脂肪酸用手性荧光衍生化试剂（1R，2R） - 和（1s，2s）-2-（2,3-持持亲性的辅助辅助辅助剂）标记。在低柱温度条件下，在ODS柱上将高达C20抗酸酯的非对映异构体衍生物分为两个峰，而具有超过C21的那些则不能被系统分离。 C30色谱柱使可对非对非对非对非洲裔衍生物的最高为C29 Anteiso酸是可能的。关于非对映异构体衍生物的洗脱顺序有经验规则，它使我们能够通过使用试剂的两个对映异构体来确定分支链羧酸的绝对构型。这种方法使得可以在从附录鞭毛藻酸酯coollia honotis和甘油甘油果仁糖S365a分离的新型神经酰胺中确定甲基支枝脂肪酸的绝对构型，并从corynebacterium aquaticum中分离出来，也可以在两种环磷酸磷酸盐的绝对构型中均可确定plakopane moielide a a的绝对构造。，一种免疫抑制海洋甲磷脂果脂。