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; 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。在这个项目中，我们开发了一种新的策略，用于通过CD Interned手性方法确定单功能化合物的绝对配置。 （1）设计了带有两个萘发色团的Achiral CD辅助。 （2）CD辅助与手性的单醇相连。 （3）将酒精部分的手性转移到CD辅助上。 （4）两个萘发色团采用了刺激性CD的手性构象。 （5）为了确定酒精的绝对构型，刺激性手性是由半经验的MO和/或经验MM方法确定的。 （6）将计算出的Inventon手性与观察到的Investon CD进行了比较。因此，这种新的CD Inveenton方法的新策略确定了各种手性单杯和单羧酸的绝对构型。2。材料科学的最终研究目标之一是构建分子机器，其中一个分子机械地用作MAC…通过外部能源更大。我们最近在第一次构造分子机器的构造方面取得了成功，分子机是一种轻型手性分子电动机，该电动机仅在光化学上仅在一方面旋转，这反映了运动分子的手性。运动旋转受光和分子手性的照射控制。3。自从我们报道了Thiacalix [4] Arenene（TCA）方便合成以来，我们研究了由桥接硫引起的独特立体化学。 （1）通过S和/或O原子与金属离子的协调固定噻烷，磺胺基和磺基calix [4]领域的构象。 （2）制备了硫酸[4]领域的所有构型异构体。 （3）通过氧化TCA的两个相邻硫酸盐来制备手性二硫酸[4]领域。 （4）通过1,3-α-Altemate-TCA的单氧化构建了新的分子手性。 （5）已研究了螯合辅助的核哲学芳香族芳族取代硫酸和磺基calix [4]领域。 （6）通过将手性酰胺引入TCA来制备GC的手性固定相。较少的