Development of open chemical systems constantly producing one of the enantiomers of chiral products

开发开放化学系统，不断生产手性产品的对映体之一

基本信息

批准号：
14540548
负责人：
ASAKURA Kouichi
金额：
$ 2.37万
依托单位：
Keio University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540548/
关键词：
Chiral symmetry breaking Chiral autocatalysis Open chemical system Crystal growth front 1,1'-Binaphthyl Asymmetric amplification Non-linear kinetic model Michaelis-Menten type intermediate 1,1-ビナフチルキラル自触媒系光学純度速度論解析 PDB

项目摘要

Homochirality in biomolecules in nature can be regarded as a chiral symmetiy breaking, a dissipative structure, that is a self-orgnization in nonequilibrium open system as a result of growth of fluctuation by irreversible dissipative processes. The kinetic model for chiral symmetry breaking was proposed about 20 years ago (D.K.Kondepudi, G.W.Nelson. Nature, 1985, 314, 438). The real chemcal system in which spontaneous generation of homochirality by following the model, hewever, has not been realized.Crystallization of 1,1'-binaphthyl from its racemic melt was studied. Chiral crystal of 1,1'-binaphthyl is crystallized when the temperature is in the range from 145 to 158℃, and the crystallization process is chirally autocatalytic (D.K.Kondepudi, J.Laudadio, K.Asakura, J.Am.Chem.Soc., 1999, 121, 1448). Temperature distribution in crystallization system was monitored and the structure of the crystal phase thus generated was characterized by X-ray diffraction. Enantiomeric excess of the cry … More stal phase generated when the temperature of the growth front was in the range from 145 to 158℃ was bimodal and its average was about 60%. The spontaneous generation of chiral asymmetry was identified as the chiral symmetry breaking in the growth front. A kinetic model to explain the mechanism was developed to investigate the condition at which racemic state becomes unstable to lead to generate homochiral state.A mechanism of asymmetric amplification, chemical reaction in which enantiomeric excess of a product is higher than that of chiral auxiliary for catalyst, was also investigated. The ultimate goal of this research is to achieve chiral symmetry breaking by following Kondepudi & Nelson's model in organic chemical reaction system. The chirally autocatalytic reaction found by Soai et al. is one of the candidate reaction (K.Soai, et al., Nature, 1995, 378, 767) Similar compounds are used for the asymmetric amplification and the chirally autocatalytic reaction. Michaelis-Menten type intemediate was found to be generated in the asymmetric amplification. Less

本质中生物分子的同Rirelity可以将其视为一种手性对称性破裂，这是一种耗散结构，这是由于不可逆转的耗散过程的波动增长而在非平衡开放系统中的一种自我识别。大约20年前提出了手性对称性破裂的动力学模型（D.K. Kondepudi，G.W.Nelson。Nature，1985，314，438）。实际的化学系统尚未实现，其中尚未实现该模型的同质产生。从其外消旋熔体中的1,1'-二磷酸的结晶是研究的。当温度在145到158至158 r的范围内，1,1'-二磷酸的手掌晶体被结晶而结晶。 J.Laudadio，K.Asakura，J.Am.Chem.Soc。，1999，121，1448）。监测结晶系统中的温度分布，并以X射线衍射为特征的晶相结构。当生长阵线的温度在145到158℃时，产生的cry的对映体过量是双峰时期产生的，其平均水平约为60％。发起人的手性不对称产生被确定为在生长方面的手性对称性破裂。开发了一种动力学模型，以调查外消旋状态变得不稳定以产生同型同种状态的条件。一种不对称扩增的机制，即化学反应，其中增强产物的可用性高于催化剂的催化剂辅助剂的可用性。这项研究的最终目标是通过遵循有机化学反应系统中的Kondepudi＆Nelson模型来实现手性对称性破坏。 Soai等人发现的手性自催化反应。是候选反应之一（K.Soai等人，Nature，1995，378，767）类似的化合物用于非对称扩增和手性自催化反应。发现Michaelis-Menten型整数是在不对称扩增中产生的。较少的