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Study on chiral discrimination mechanism upon crystallization and its application to development of novel general optical resolution method.

结晶时手性判别机制的研究及其在新型通用光学拆分方法开发中的应用。

基本信息

批准号：
09450330
负责人：
SAIGO Kazuhiko
金额：
$ 8.96万
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：
1997
资助国家：
日本
起止时间：
1997 至 2000
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-09450330/
关键词：
Optical Resolution Diastereomeric Method Crystal Engineering Hyrogen Bond ジアステレオマ-塩法

项目摘要

In order to clarify the mechanism of optical resolution upon crystallization and to rationally design a tailor-made resolving agent, the optical resolution of systematically selected racemates with series of resolving agents have been studied. As a result of comparison of the crystal structures between the less- and more-soluble diastereomeric salts, it has been found that the lesssoluble salts were effectively stabilized by hydrogen-bonding, CH…π, and van der Waals interactions. On the basis of this result, we desinged 2-naphthylglycolic acid, cis-1-amino-2-indanol, etc., in which a hydrogen-bonding group and other interacting group (s) were suitably placed to stabilize the less-soluble salts. In fact, these resolving agents had excellent resolution ability for 1-arylethylamines and 2-arylalkantoic acids, respectively. Thus, we have succeeded in designing novel resolving agents on the basis of the concept of crystal engineering.On the other hand, we focused on the fact that there is a similarity in crystal structure between a conglomerate salt of a chiral amine with an achiral carboxylic acid and a less-soluble diastereomeric salt which crystallizes exclusively during optical resolution. Then, we checked the crystal structures of the salts of racemic amine with racemic carboxylic acid, in which one of the enantiopure components is a good resolving agent for the other component. As a result, it was found that conglomerate tends to be formed in extremely high probability in such a system.

为了阐明结晶过程中光学拆分的机理，合理设计拆分剂，本文系统地研究了系列拆分剂对消旋体的光学拆分。作为比较难溶和更难溶的非对映体盐之间的晶体结构的结果，已经发现难溶的盐通过氢键、CH. π和货车范德华相互作用而有效地稳定。在此基础上，我们设计了2-萘乙酸、顺-1-氨基-2-茚满醇等，其中适当地放置氢键基团和其它相互作用基团以稳定难溶盐。实际上，这些拆分剂分别对1-芳基乙胺和2-芳基链烷酸具有优异的拆分能力。因此，我们已经成功地设计了新的拆分剂的晶体工程的概念的基础上，另一方面，我们专注于一个事实，即有一个相似的晶体结构之间的聚集盐的手性胺与非手性羧酸和一个不太可溶的非对映体的盐，结晶只在光学拆分。然后，我们检查了外消旋胺与外消旋羧酸的盐的晶体结构，其中一个对映体纯的组分是另一个组分的良好拆分剂。结果发现，在这样的系统中，砾岩倾向于以极高的概率形成。