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

• 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

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.视紫红质中视网膜发色团的绝对构象是理解视觉信号转导过程的核心问题。哥伦比亚大学的Nakanishi教授等人对具有3/7元环系统的11-顺式锁定手性视网膜类似物（1）的研究报告了视紫红质中发色团的12-13单键周围的绝对扭转。然而，1的绝对构型与CD计算结果不一致。为了明确地确定1的绝对立体化学，我们将“手性邻苯二甲酸法”应用于3/7元醇。双环[5.1.0]辛-2，6-二醇（顺式-2）与手性邻苯二甲酸二氯酯（-）-3缩合，得到酯的非对映体混合物（4），其易于在硅胶上用HPLC分离。由酯4 B制备的对溴苯甲酸酯（+）-（5）结晶为适合于X射线衍射的单晶。（+）-（5）的（1 S，2 R，7 R）构型由X-r确定 ...更多信息 ay Bijvoet方法。作为近年来开发的生物活性化合物和手性有机材料的基础信息，我们正在构建手性数据库“手性世界”。“为了收集大量的CD数据，我们邀请了Keiserlestern大学的Kuball教授，还派Harada教授去那里，我们开发了CD数据库格式来规范这些数据。3.作为与伊利诺伊大学Pirkle教授的联合工作，通过手性邻苯二甲酸方法对各种邻位取代的二芳基甲醇进行了对映体拆分，如下：（1）外消旋醇与手性邻苯二甲酸的酯化，（2）通过HPLC在硅胶上分离形成的酯的非对映体混合物，和（3）从分离的酯中回收对映体纯醇。用X射线晶体学方法，以樟脑磺内酰胺为绝对构型的内标物，确定了手性邻苯二甲酸二芳基甲醇酯的绝对构型。少

项目成果

H.Goto,N,Harada: "Absolute Configuration of Chiral Fullerenes and Covalent Derivatives from Their Calculated Circular Dichroism." J.Chem.Soc.,Perkin 2. 1719-1723 (1998)

H.Goto,N,Harada：“根据计算的圆二色性计算手性富勒烯和共价衍生物的绝对构型。”

N.Koumura,N.Harada: "Photochemistry and Absolute Stereochemistry of Unique Chiral Olefins,trans-and cis-1,1',2,2',3,3',4,4'-Octahydro-3,3'-dimethyl-4,4'-biphenanthrylidenes." Chem Lett.1151-1152 (1998)

N.Koumura、N.Harada：“独特手性烯烃的光化学和绝对立体化学，反式和顺式-1,1,2,2,3,3,4,4-八氢-3,3-

R.W.J.Zijlstra,N.Harada: "Chemistry of Unique Chiral Olefins.Part 4.Theoretical Studies of the Racemization Mechanism of trans-and cis-1,1',2,2',3,3',4,4'-Octahydro-4,4'-biphenanthrylidenes." J.Org.Chem.in press. (1999)

R.W.J.Zijlstra，N.Harada：“独特手性烯烃的化学。第4部分。反式和顺式-1,1,2,2,3,3,4,4-八氢外消旋化机制的理论研究

N.Harada: "Molecular Chirality by Isotopic Substitution. Synthesis, Absolute Configuration, and CD Spectra of ^<13>C Substituted Chiral Diphenylmethanol"J.Phys.Org.Chem.. 13. 422-425 (2000)

N.Harada：“同位素取代的分子手性。13C取代的手性二苯甲醇的合成、绝对构型和CD光谱”J.Phys.Org.Chem.. 13. 422-425 (2000)

R.W.J.Zijlstra, N.Harada: "Chemistry of Unique Chiral Olefins.4.Theoretical Studies of the Racemization Mechanism of trans- and cis-1,1',2,2',3,3',4,4'-Octahydro-4,4'-biphenanthrylidenes"J.Org.Chem.. 64. 1667-1674 (1999)

R.W.J.Zijlstra，N.Harada：“独特手性烯烃的化学。4.反式和顺式1,1,2,2,3,3,4,4-八氢-的外消旋化机制的理论研究