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转导过程的核心问题。Nakanishi教授等人在研究具有3/7元环体系的11顺锁手性视网膜类似物(1)时报道了视紫质中发色团的12-13单键周围的绝对扭曲。哥伦比亚大学。但是，1的绝对构型与CD计算得到的构型不一致。为了明确地确定1的绝对立体化学性质，我们对3/7元醇应用了“手性邻苯二甲酸法”。双[5.1.0]辛烷-2,6-二醇（syn-2）与手性二氯邻苯二酸(-)-3缩合得到酯类非对映体混合物(4)，该混合物易于在硅胶上用高效液相色谱分离。由4B酯制备的对溴苯甲酸酯(+)-(5)结晶为单晶，适合x射线衍射。（+）-(5)的（1S, 2R, 7R）构型由X-r…More ay Bijvoet方法明确确定。随着近年来生物活性化合物和手性活性有机材料的基础信息的发展，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Keiserslautern大学的Kuball教授和Harada教授，并开发了CD数据库格式来规范化这些数据。与美国伊利诺斯大学的Pirkle教授合作，用手性邻苯二甲酸法对不同的邻取代二芳基甲醇进行了对映分解：(1)外消旋醇与手性邻苯二甲酸的酯化反应；(2)在硅胶上用高效液相色谱法分离形成的酯的非对映异构体混合物；(3)从分离的酯中回收对映纯醇。采用x射线结晶学方法，用康法舒坦部分作为绝对构型的内标，确定了邻苯二甲酸酯的绝对构型。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