Development of Highly Sensitive Analytical Systems to Determine the Absolute Configuration of Chiral Compounds

开发高灵敏度分析系统以确定手性化合物的绝对构型

• 批准号: 03556014
• 负责人: MEGURO Hiroshi
• 金额: $ 8.83万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03556014/
• 关键词: Absolute configuration; Optical purity; Chirality; Fluorescent reagent; (+)-TBMB carboxylic acid; High performance liquid chromatography; chiral derivatization; D, L-sugar; D, L-amino acid; D, L-glycerol; 発ケイ光性試薬; 高速液体クロマトグラフィー; 光学活性化合物; キラルカ

With aims to develop highly sensitive ways to determine the absolute configurations of chiral molecules, new type of chiral derivatizing agents, (+)-TBMB and (+)-TBB carboxylic acids were designed and prepared. The absolute configurations of the former was determined to be (2S) by X-ray analysis of the L-phenylalanie derivative. They were designed to have a CD (circular dichroism) chromophore, isolated Me groups and fluorescent in the bodies which can be effectively used in the CD, NMR and HPLC analyzes to determine the absolute configuration and the optical purity of chiral molecules.Targets for applying these two reagents were directed to three biomolecules, carbohydrates, amino acids and glycerolipids. The analytical conditions were investigated for the derivatization, purification, separations and detections for each. Consequently, simple and highly sensitive methods were established to analyze the D, L-isomers. For sugars and amino acids, NMR and HPLC were effectively employed in the system. For glycerolipids, circular dichroism (CD) based on exciton chirality way was coupled with HPLC system to build a simultaneous system to determine the absolute configuration and the optical purity. This system was employed in the study on the stereochemistries of lipase-catalyzed hydrolysis of glycerides.

旨在开发高度敏感的方法来确定手性分子的绝对构型，新型的手性衍生剂，（+） - TBMB和（+） - TBB羧酸的设计和制备。通过X射线分析L-苯基烷衍生物的X射线分析，确定了前者的绝对构型。它们被设计为具有CD（圆形二分法）发色团，将我分离出来，并在体内隔离并有效地用于CD，NMR和HPLC分析中，以确定手性分子的绝对构型和光学纯度。将这两种辐射用于将这两种辐射施加到三种生物中，并将其定向到三种生物中，并将其定向。研究了分析条件，以实现每个分析条件的衍生化，纯化，分离和检测。因此，建立了简单且高度敏感的方法来分析D，L-异构体。对于糖和氨基酸，NMR和HPLC有效地在系统中使用。对于甘油脂质，基于激子手性方法的圆二色性（CD）与HPLC系统结合起来，以构建同时的系统，以确定绝对配置和光学纯度。该系统用于研究脂肪酶催化水解甘油三酸酯的立体化体。

项目成果

Yoshihiro Nishida: "Determination of the Absolate Configuration of monosaccharicles Wing (+)or(-)2-tert-butyl-2methyl-1.3-benzodioxole-4-Carloxpylie Acid and Nigh-xeselution ^1H-n.m.r.Spectnoscopy" Carlohyarate Research. 218. 63-73 (1991)

Yoshihiro Nishida：“单糖翼 ( ) 或 (-)2-叔丁基-2甲基-1.3-苯并二氧杂环戊烯-4-Caroxpylie 酸的绝对构型的测定和 Nigh-xeselution ^1H-n.m.r.光谱学” Carlohyarate Research。

H.Uzawa et al.: "A Convenient evaluation of the stereo selectivity of lipase-catalyzed hydrolysis of tri-O-acylglycerols" Biochim.Biophys.Acta. 1169. 165-168 (1993)

H.Uzawa 等人：“脂肪酶催化三-O-酰基甘油水解立体选择性的便捷评估”Biochim.Biophys.Acta。

J.H.Kim et al: "A Highly Sensitive HPLC Method for the Determination of the Absolute configuration and the Optical Purity of Di-O Acyl Glycerd" J.Chromatography. (印刷中). (1994)

J.H.Kim 等人：“测定二-O 酰基甘油的绝对构型和光学纯度的高灵敏度 HPLC 方法”J.Chromatography（出版中）。

Hirotaka Uzawa, Hiroshi Ohrui, Hiroshi Meguro: "Developments of Practical Methods to Determine the Absolute Configurations of Chiral Glycerols" Kagaku & Seibutsu (Japanese). 29. 394-398 (1991)

Hirotaka Uzawa、Hiroshi Ohrui、Hiroshi Meguro：“确定手性甘油绝对构型的实用方法的发展” Kagaku

Yoshihiro Nishida, Masayuki Abe, Hiroshi Ohrui and Hiroshi Meguro: "(+)-Tert-butyl-1, 3-benzodioxole-4-carboxylic acid : Fluorescent Chiral Carboxylic Acid with a 1, 3-Benzodioxole Skeleton" Tetrahedron : Asymmetry. 4. 1431-1434 (1993)

Yoshihiro Nishida、Masayuki Abe、Hiroshi Ohrui 和 Hiroshi Meguro：“( )-叔丁基-1, 3-苯并二氧杂环戊烯-4-羧酸：具有 1, 3-苯并二氧杂环戊烯骨架的荧光手性羧酸”四面体：不对称性。