Construction and Control of Helical Supramolecules Based on Sequential Information of Carbon-Chains

十多年来，我们一直在研究类固醇的包涵性化合物。本课题旨在利用手性碳链序列信息构建和控制包合晶体中的螺旋超分子。这样的研究可能使我们能够建立手性碳链化合物（如类固醇）的分子信息和表达概念。结果总结如下：1。我们合成了许多甾体衍生物，包括顺序信息，从市售的胆酸和去氧胆酸开始。这些化合物被发现在大多数情况下形成由螺旋组合组成的包合晶体。利用一百多个来宾对甾体宿主的包合行为进行了检验。我们确定了包含的来宾组件的范围。每个主机的作用域因情况而异。我们从大小、形状、手性和极性等方面积累了必要的包合物数据，以探讨主客体络合的可能机制。我们用粉末和单晶x射线晶体学分析了所得的包合物，发现了50多种螺旋结构的包合物。利用各种软件从螺旋结构的各个方面对螺旋总成进行了分析。例如，分子图形学的研究帮助我们评估了原始分子结构与最终螺旋结构之间的关系。我们证实了氢键基团之间的多重组合可能在决定螺旋结构中起重要作用。现在我们认为，手性碳链化合物由于其表面两亲性，倾向于在可分散氢键和范德华相互作用的基础上构建全面的螺旋结构。

We have been studying on inclusion compounds of steroids over ten years. In this research project we aim to construct and control helical supramolecules in inclusion crystals on the basis of sequential information of chiral carbon-chains. Such a study may enable us to establish the concept of molecular information and expression of chiral carbon-chain compounds, such as steroids. The results are summarized as follows ;1. We synthesized many steroidal derivatives involving sequential information, starting from commercially availabe cholic and deoxycholic acids. Such compounds were found to form inclusion crystals composed of helical assemblies in most of the cases.2. The inclusion behaviors of the steroidal hosts were checked by using more than one hundred guests. We determined a scope of the guest components included. The scope for each host varied from one case to another. We accumulated inclusion data necessary for considering possible mechanism of the host-guest complexation from a viewpoint in size, shape, chirality and polarity.3. We analyzed the resulting inclusion compounds by means of powder and single crystal X-ray crystallography, leading to the finding of over fifty helical structures of the inclusion compounds. We analyzed the helical assemblies from various aspects of the helical structures by using various softwares. For example, molecular graphics study helped us to evaluate a relation between the original molecular structures and the resulting helical structures.4. We confirmed that multiple combinations among the hydrogen-bonding groups may play an important role in determining the helical structures. Now we believe that chiral carbon-chain compounds tend to construct comprehensive helical assemblies on the basis of diversible hydrogen bonds and van der Waals interaction due to facially amphiphilicity.