Construction and Application of Chiral Space with Axially Asymmetric Bianthryls

以9,9′-二苯基为结构，设计了新的轴向手性芳香化合物，并对其手性性质、晶体中的手性空间特征和动态立体化学进行了研究。手性9,9'-二羧酸衍生物，2,2'-或3,3'-二羧酸衍生物的对映体通过非对映体盐分离。通过x射线结构分析确定了手性轴的绝对立体化学性质。用TDDFT方法可以较好地再现所观察到的圆二色性（CD）光谱。对2,2′-二羧酸酯进行包合实验。对映纯甲酯包含广泛的有机小分子，而外消旋化合物仅包含苯，相应的苯基酯没有包合能力。在x射线结构的基础上讨论了这些差异。旋光性9,9'-二烷基旋光体。取代的9,9'-二烯基旋旋体和旋旋体作为中酒石酸的立体化学模型被分离出来。通过本研究，我们重新审视了“绝对构象”这一术语。为了限制乙炔轴上的旋转，制备了两端分别含有9-蒽基、9-三烷基或1-萘基的位阻炔，当引入大体积取代基时，通过核磁共振可以观察到其动力学过程。二（9-三烷基）乙烷衍生物的旋转势垒最高为77 kJ/mol。用x射线结构和动力学数据考察了取代基对旋转势垒的影响。

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.