Construction and Application of Chiral Space with Axially Asymmetric Bianthryls

基于9，9 ′-联蒽基的结构设计了新的轴向手性芳香族化合物，并对其手性光学性质、晶体中手性空间特征和动态立体化学进行了研究。1.手性9，9 ′-联蒽基二羧酸衍生物，2，2 ′-和3，3 ′-二羧酸衍生物的对映体通过非对映体盐拆分。通过X-射线结构分析确定了手性轴附近的绝对立体化学。所观察到的圆二色性（CD）光谱合理地再现TDDFT方法。对2，2 '-二羧基酯进行了包合实验。对映体纯的甲酯包含了许多小分子的有机物，而外消旋的化合物只包含苯，相应的苯酯没有表现出包结能力。这些差异在X-射线结构的基础上进行了讨论。2.光学活性的9，9 '-双三酰基旋转异构体。分离了光学惰性和活性的取代9，9 '-联三苯酰的旋转异构体作为meso-酒石酸的立体化学模型。3.为限制炔轴的旋转，我们制备了两端带有9-蒽基、9-三蝶基或1-萘基的空间位阻炔，当引入大体积取代基时，通过核磁共振谱可以观察到其动力学过程。最高的旋转势垒为77 kJ/mol，观察到在二（9-triptycyl）乙炔衍生物。通过X射线结构和动力学数据研究了取代基对转动势垒的影响。

New axially chirai aromatic compounds were designed based on the structure of 9,9'-bianthryl, and their chiroptical properties, features of chiral spaces in crystals, and dynamic stereochemistry were studied.1.Chiral 9,9'-bianthryldicarboxylic acid derivatives, Enantiomers of 2,2'-or 3,3'-dicarboxylic acid derivatives were resolved via diastereomeric salts. The absolute stereochemistry about the chiral axis was determined by the X-ray structural analysis. The observed circular dichroism(CD) spectra were reasonably reproduced by the TDDFT method. The inclusion experiments were carried out for the 2,2'-dicarbocxylie esters. The enantiopure methyl ester includes a wide range of smalt organic molecules, while the racemic compound includes only benzene, The corresponding phenyl ester showed no inclusion ability. These differences are discussed on the basis of X-ray structures.2.Optically active 9,9'-bitriptycyl rotamers. Optically inactive and active rotamers of substituted 9,9'-bitriptycyls were isolated as a stereochemical model of meso-tartaric acid. We revisited the term of "absolute conformation" through this study.3.Restricted rotation about acetylenic axis, To restrict the rotation about acetylenic axis, sterically hindered alkynes with 9-anthryl, 9-triptycyl, or 1-naphthyl groups at the both termini were prepared, When bulky substituents Were introduced, the dynamic processes could be observed by the NMR. The highest rotational barrier was 77 kJ/mol observed in a di(9-triptycyl)ethyne derivative. The substituent effects on the rotational barriers are examined by the X-ray structure and the kinetic data.