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Chasing chirality recognition reaction in the solid-state

追逐固态手性识别反应

基本信息

批准号：
10554045
负责人：
KURODA Reiko
金额：
$ 8.51万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

In the solid state, molecules often behave differently from solution state. We have found that a photocyclization reaction of a non-chiral compound in an inclusion compound with an optically active host, enantio-selectively produced a chiral product. This is in sharp contrast to the same reaction carried out in solution state where racemic mixture was produced. We have revealed the reason behind the high enantio-selectivity by X-ray structural work. The reaction process was followed by X-ray single-crystal diffractometry using one single-crystal. The structure and location within the unit-cell of the host molecule hardly changed by the reaction and the hydrogen bonds between the host and the guest molecules were kept. Solid-state CD exhibited a series of spectra with isosbestic points during the reaction process.To detect solid-state chiroptical properties, it is necessary to observe CD in the solid state. Solid-state suffers from artifacts due to its large anisotropy. We have designed and made a solid-state dedicated CD spectrophotometer to remove artifacts to obtain true CD.The instrument houses a good quality phtomultiplier and a photoelastic modulator, and an analyzer which can be inserted or removed from the optical path easily. Sample and the analyzer can be rotated easily. Tow lock-in-amplifiers are installed to record 50 and 100 kHz signals. This method was applied to single crystals and films.

在固态下，分子的行为通常与溶液状态不同。我们已经发现，在包合物中的非手性化合物与光学活性主体的光环化反应，对映选择性地产生手性产物。这与在溶液状态下进行的产生外消旋混合物的相同反应形成鲜明对比。通过X-射线结构分析，揭示了高对映体选择性的原因。反应过程通过使用一个单晶的X射线单晶衍射法进行跟踪。反应几乎不改变主体分子的结构和在晶胞内的位置，保持了主体分子和客体分子之间的氢键。固态CD在反应过程中呈现出一系列具有等吸光点的光谱，要研究固态CD的手性性质，必须观察固态CD。固态由于其大的各向异性而遭受伪影。我们设计并制作了一台固态专用CD分光光度计，用于去除伪影以获得真正的CD。该仪器内有一个高质量的光电倍增管和一个光弹调制器，以及一个可以很容易地插入或从光路中取出的分析器。样品和分析仪可以轻松旋转。两个锁定放大器安装记录50和100千赫的信号。这种方法适用于单晶和薄膜。