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

基本信息

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

项目摘要

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，我们开发了一种通过环糊精激子手性方法测定单官能化合物绝对构型的新策略 (1) 设计了具有两个萘发色团的非手性环糊精辅助剂 (2) 设计了环糊精辅助剂。 (3)将醇部分的手性转移至CD助剂上。(4)两个萘发色团。 (5) 为了确定醇的绝对构型，通过半经验 MO 和/或经验 MM 方法确定激子手性。 (6) 将计算的激子手性与观察到的激子 CD 进行比较。因此，通过CD激子方法的这种新策略确定了各种手性一元醇和一元羧酸的绝对构型。2．我们最近成功构建了第一个分子机器，即光动力手性分子马达，它仅在一个方向上进行光化学旋转。 -方向反映了电机分子的手性。电机旋转由光的照射和分子手性控制。3．研究了桥硫产生的独特立体化学（1）硫杂芳烃、亚磺酰基芳烃和磺酰基杯[4]芳烃的构象通过S和/或O原子与金属离子的配位固定。 (3)通过氧化两个相邻的二亚磺酰杯[4]-芳烃制备手性二亚磺酰杯[4]-芳烃(4) 通过 1,3-altemate-TCA 的单氧化构建了新的分子手性。 (5) 研究了亚磺酰基和磺酰基杯[4]芳烃的螯合辅助芳香取代反应。通过将手性酰胺引入 TCA Less 来制备 GC 手性固定相。