Development of CD Method and Application to Stereochemistry

CD方法的发展及其在立体化学中的应用

基本信息

批准号：
10045022
负责人：
HARADA Nobuyuki
金额：
$ 4.29万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10045022/
关键词：
CD Spectra Organic Stereochemistry Visual Transduction Process Retinal Analogues CD Database Chiral Phthalic Acid Method X-ray crystallography Chiral Substituted Diaryl Methanols 立体配座レチナールレチナール類緑体円二色性スペクトル法キラル分子絶対配置 CD補助基

项目摘要

1. The absolute conformation of the retinal chromophore in rhodopsin is a central problem for understanding the visual transduction process. The absolute twist around the 12-13 single bond of the chromophore in rhodopsin has been reported on studies with 11-cis-locked chiral retinal analogues (1) with 3/7 membered ring system by Prof. Nakanishi et al. Columbia University. However, the absolute configuration of 1 disagrees with that obtained by the CD calculation. To determine the absolute stereochemistry of 1 in an unambiguous manner, we have applied "the chiral phthalic acid method" to 3/7 membered alcohol. Bicyclo [5.1.0] octan-2,6-diol (syn-2) was condensed with chiral dichlorophthalic acid (-)-3 to yield a diastereomeric mixture of esters (4), which was easily separated by HPLC on silica gel. p-Bromobenzoate (+)-(5) prepared from ester 4B crystallized as single crystals suitable for X-ray diffraction. The (1S, 2R, 7R) configuration of (+)-(5) was unambiguously determined by the X-r … More ay Bijvoet method.2. As the fundamental information of bioactive compounds and chiroptically active organic materials recently developed, we are constructing the chirality database, "Chiral World." To collect many CD data, we have invited Prof. Kuball, University of Keiserslautern, and also sent Prof. Harada there, and we have developed the CD database format to normalize these data.3. As the joint work with Prof. Pirkle, University of Illinois, various o-substituted diaryl methanols were enantioresolved by the chiral phthalic acid method as follows ; (1) esterification of racemic alcohols with chiral phthalic acid, (2) separation of a diastereomeric mixture of the esters formed by HPLC on silica gel, and (3) recovery of enantiopure alcohols from the separated esters. The absolute configurations of chiral phthalic acid esters of o-substituted diaryl methanols were unambiguously determined by the X-ray crystallography using the campharsultam moiety as the internal standard of absolute configuration. Less

1。视视蛋白的绝对同意是理解视觉转导过程的核心问题。但是，哥伦比亚大学教授的3/7构件。 -3产生酯（4）的酯混合物（4），在X射线衍射上很容易通过HPLC分离。 x-r…更多的bijvoet方法。2。 3我们开发了TAT ASE格式以使这些数据归一化。3。 2）由HPLC在硅胶上形成的酯的非对映异构体的分离，并（3）从分别估计的酯中回收对映体醇的绝对构型。射线晶体仪使用Campharsultam Ess