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

1. 在这个项目中，我们开发了一种新的策略来确定单功能化合物的绝对构型的CD激子手性方法。(1)设计了具有两个萘发色团的非手性CD助剂。(2)将CD助剂与手性单醇连接。(3)醇部分的手性转移到CD助剂上。(4)两个萘发色团形成手性构象，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方法测定了激子手性。(6)将计算得到的激子手性与观测到的激子CD进行了比较，从而用这种新的CD激子方法确定了各种手性单醇和单羧酸的绝对构型。材料科学的终极研究目标之一是构建分子机器，在这种机器中，一个分子就像一个机器一样机械地工作。我们最近成功地首次构建了一个分子机器，一个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。电机的旋转是由光的照射和分子手性控制的。自从我们报道了硫环芳烃（thacalix [4]arene， TCA）的快速合成以来，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原子与金属离子的配位固定了羟基、亚砜基和磺酰基杯芳烃的构象。(2)制备了亚砜杯[4]芳烃的所有构型异构体。(3)由相邻的两个TCA硫氧化制得手性二亚砜杯[4]-芳烃。(4) 1,3-丙二醇-三羧酸单氧化法构建了新的分子手性。(5)研究了螯合辅助亲核芳烃取代亚砜基和磺酰基杯芳烃。(6)在TCA中引入手性酰胺，制备了气相色谱用手性固定相。少

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