Development of New CD Methods for Determining the Absolute Stereochemistry of Chiral Molecules

开发测定手性分子绝对立体化学的新 CD 方法

• 批准号: 10208202
• 负责人: HARADA Nobuyuki
• 金额: $ 13.06万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (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/grant/KAKENHI-PROJECT-10208202/
• 关键词: CD Spectra; CD Exciton Method; Absolute Stereochemistry; Molecular Machine; Light-Powered Chiral Molecular Motor; Thiacalixarene; Optically Active Sulfoxides; Molecular Asymmetry; キラル分子モーター; ツメ歯車効果; 有機立体化学; 不斉カリックスアレーン; 不斉識別; 分子キラリティー; 円二色性法

1. In this project, we have developed a new strategy for determining the absolute configuration of mono- functional compounds by the CD exciton chirality method. (1) An achiral CD auxiliary with two naphthalene chromophores was designed. (2) The CD auxiliary was connected with chiral mono-alcohols. (3) The chirality of the alcohol part was transferred to the CD auxiliary. (4) Two naphthalene chromophores took a chiral conformation generating exciton CD. (5) To determine the absolute configuration of the alcohol, the exciton chirality was determined by the semi-empirical MO and/or empirical MM methods. (6) The calculated exciton chirality was compared with the observed exciton CD. The absolute configurations of various chiral mono-alcohols and mono-carboxylic acids have been thus determined by this new strategy of the CD exciton method.2. One of the ultimate research goals of material science would be the construction of molecular machines, where one molecule mechanically works as a mac … More hine by external energy sources. We have recently succeeded in the first construction of a molecular machine, a light-powered chiral molecular motor, which photochemically rotates only in one-direction reflecting the chirality of the motor molecule. The motor rotation is controlled by the irradiation of light and molecular chirality.3. Since we reported facile synthesis of thiacalix[4]arene (TCA), we have studied the unique stereochemistry arising from the bridging sulfur. (1) The conformations of thia-, sulfinyl-, and sulfonylcalix[4]arenes were fixed by coordination of S and/or O atoms to metal ion. (2) All configurational isomers of sulfinylcalix[4]arenes were prepared. (3) Chiral disulfinylcalix[4]-arenes were prepared by oxidation of two adjacent sulfurs of TCA. (4) New molecular chirality was constructed by mono-oxidation of 1,3-altemate-TCA. (5) Chelation-assisted nucleophilic aromatic substitution to sulfinyl- and sulfonylcalix[4]arenes has been studied. (6) Chiral stationary phases for GC were prepared by introducing chiral amides into TCA. Less

1.在本项目中，我们发展了一种用CD激子手性方法确定单功能化合物绝对构型的新策略。(1)设计了一种含两个发色团的无手性CD助剂。(2)CD辅基与手性一元醇连接。(3)将乙醇部分的手性转移到CD辅助剂上。(4)两个发色团均为手性构象，产生激子CD。(5)为了确定醇的绝对构型，用半经验MO和/或经验MM方法确定了激子手性。(6)将计算得到的激子手性与观察到的激子CD进行了比较。通过CD激子方法的这一新策略，确定了各种手性一元醇和一元羧酸的绝对构型。材料科学的最终研究目标之一将是建造分子机器，其中一个分子机械地作为mac…工作。更多地依靠外部能源。我们最近首次成功地建造了一台分子机器，一种光动力的手性分子马达，它只在一个方向上光化学旋转，反映了马达分子的手性。电机的转动受光的照射和分子手性的控制。自从我们报道了硫杂杯[4]芳烃(TCA)的简单合成以来，我们研究了由硫桥联而产生的独特的立体化学。(1)硫、亚磺基和磺酰杯[4]芳烃的构象是通过S原子和/或O原子与金属离子配位而固定的。(2)合成了亚磺酰杯[4]芳烃的所有构型异构体。(3)由TCA的两个相邻硫化物氧化制备了手性二磺基杯[4]-芳烃。(4)1，3-天冬氨酸-三氯乙酸单氧化构筑了新的分子手性。(5)研究了亚磺基和磺酰杯[4]芳烃的螯合辅助亲核取代反应。(6)将手性酰胺引入到TCA中，制备了手性固定相。较少

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