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。视视紫红质中视网膜成色团的绝对构象是理解视觉转移过程的核心问题。 Nakanishi等人教授围绕着Rhodopsin中发色团的12-13个单键的绝对扭曲（1）与3/7构建的环系统的研究。哥伦比亚大学。但是，与CD计算获得的1个不同意的绝对配置。为了以明确的方式确定1的绝对立体化学，我们将“手性邻苯二甲酸法”应用于3/7成员的酒精。 Bicyclo [5.1.0]用手性二氯乙酸（ - ）-3凝结八丹-2,6-二醇（Syn-2），以产生酯的非对映聚体混合物（4），该混合物在硅胶上很容易通过HPLC分离。 p-溴苯酸盐（+） - （5）由酯4b制备的单晶体，适合于X射线衍射。（1s，2r，7r）（（+） - （5）的（5）的配置是通过X-R…More Ay Bijvoet方法明确确定的。2。随着最近开发的生物活性化合物和手性有机材料的基本信息，我们正在构建手性数据库“手性世界”。为了收集许多CD数据，我们邀请了Keiserslautern大学Kuball教授，并将Harada教授发送到了那里，并且我们开发了CD数据库格式以正常化这些数据。3。当与伊利诺伊大学的Pirkle教授的联合合作时，手性邻苯二甲酸法对各种O取代的二二二元甲醇进行了映射，如下所示；（1）用手性邻苯二甲酸酯化外消旋醇，（2）由HPLC在硅胶上形成的酯的非映射混合物分离，（3）（3）从分离的酯中回收映体醇。用campharsultam部分通过X射线晶体学作为绝对构型的内标，可以通过X射线晶体学明确确定O-叠定二释放甲醇的手性邻苯二甲酸酯的绝对构型。较少的