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

1. 在这个项目中，我们开发了一种通过圆二色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CD辅助剂。 (2)CD助剂与手性一元醇连接。 (3)醇部分的手性转移到CD助剂上。 (4)两个萘发色团呈手性构象，产生激子CD。 (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。通过CD激子法这一新策略，确定了各种手性一元醇和一元羧酸的绝对构型。 2．材料科学的最终研究目标之一是构建分子机器，其中一个分子通过外部能源像机器一样机械地工作。我们最近成功构建了第一个分子机器，即光驱动的手性分子马达，它仅在一个方向上进行光化学旋转，反映了马达分子的手性。电机的旋转是通过光的照射和分子手性来控制的。3．自从我们报道了硫杂[4]芳烃（TCA）的简便合成以来，我们研究了桥联硫产生的独特立体化学。 (1)硫杂、亚磺酰基和磺酰基杯[4]芳烃的构象通过S和/或O原子与金属离子的配位固定。 (2)制备了亚磺酰杯[4]芳烃的所有构型异构体。 (3)通过TCA的两个相邻硫的氧化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]芳烃的螯合辅助亲核芳香取代反应。 (6)将手性酰胺引入TCA中制备GC手性固定相。较少的

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