Correlation between the molecular structures and thermodynamic parameters of chiral recognition on Host-Guest complexation

主客体络合手性识别的分子结构与热力学参数的相关性

• 批准号: 12640518
• 负责人: HIROSE Keiji
• 金额: $ 1.86万
• 依托单位: OSAKA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640518/
• 关键词: Chiral Recognition; Crown Ether; Amine; Optically Active; Enthalpy; Entropy; Temperature Dependence; Criteria Of Molecular Design

In the cases of many complexations of crown ethers with amines, there is a linear relationship between 1n K and 1/T, which is called the van't Hoff relationship. Based on the van't Hoff relationship, the enthalpy and the entropy can be obtained quantitatively. In addition to an ordinary adopted molecular design based on qualitative host-guest complimentarity judged by a steric hindrance and a fittability between the size of cavity and that of substrate, novel criteria based on the enthalpy and entropy were thought to be contribute to create the precise molecular design of host. Here I extended this idea to a chiral recognition phenomena. I carried out this research as following three steps.(1) The syntheses of optically active artificial hosts and guests, which are correlated by the structural similarity.(2) Measurements of binding constants in the complexation between series of hosts and chiral amines.(3) Investigation of molecular recognition mechanism thinking the thermodynamic parameters.Novel six hosts and both enantiomers of 3 chiral amines were prepared, the measurements of binding constants in the complexation between part of the host-guest combinations were carried out. And the results are published under the consideration of thermodynamic parameters.

在冠醚与胺的许多络合物的情况下，1 n K与1/T之间存在线性关系，称为范特霍夫关系。根据范特霍夫关系式，可以定量地求出焓和熵。除了基于空间位阻和腔体尺寸与基底尺寸之间的适合性判断的定性主客体互补性的常规分子设计外，基于焓和熵的新标准被认为有助于创建精确的主体分子设计。在这里，我把这个想法扩展到手性识别现象。本研究分三个步骤进行。(1)光学活性人工主体和客体的合成，通过结构相似性进行关联。(2)系列主体分子与手性胺络合作用的结合常数测定。(3)从热力学参数探讨分子识别机理：合成了6种新型主体和3种手性胺的两种对映体，测定了部分主体-客体化合物之间的络合常数。并在考虑热力学参数的情况下给出了计算结果。

项目成果

Keiji Hirose, Kazuko Ogasahara, Kazuyuki Nishioka, Yoshito Tobe, and Koichiro Naemura: "Enantioselective complexation of phenolic crown ethers with chiral aminoethanol derivatives : effects of substituents of aromatic rings of hosts and guests on complexa

Keiji Hirose、Kazuko Ogasahara、Kazuyuki Nishioka、Yoshito Tobe 和 Koichiro Naemura：“酚冠醚与手性氨基乙醇衍生物的对映选择性络合：主体和客体芳环取代基对络合物的影响

Masami Sawada, Kouji Hagita, Hiroyuki Imamura, Hiroyuki Tabuchi, Shinya Yodoya, Maki Umeda, Yoshio Takai, Hitoshi Yamada, Hiroshi Yamaoka, Keiji Hirose, Yoshito Tobe, Toshikazu Tanaka, Shigetoshi Takahashi: "Chiral Recognition Ability of Crown Ethers towa

Masami Sawada、Kouji Hagita、Hiroyuki Imamura、Hiroyuki Tabuchi、Shinya Yodoya、Maki Umeda、Yoshio Takai、Hitoshi Yamada、Hiroshi Yamaoka、Keiji Hirose、Yoshito Tobe、Toshikazu Tanaka、Shigetoshi Takahashi：“冠醚的手性识别能力 towa

Keiji Hirose, Kazuko Ogasahara, Kazuyuki Nishioka, Yoshito Tobe, Koichiro Naemura: "Enantioselective complexation of phenolic crown ethers with chiral aminoethanol derivatives : effects of substituents of aromatic rings of hosts and guests on comoplexatio

Keiji Hirose、Kazuko Ogasahara、Kazuyuki Nishioka、Yoshito Tobe、Koichiro Naemura：“酚类冠醚与手性氨基乙醇衍生物的对映选择性络合：主体和客体芳环取代基对络合的影响

Keiji Hirose, Hiroyuki Naka, Masashi Yano, Sozaburo Ohashi, Koichiro Naemura and Yoshito Tobe: "Improvement of enantioselectivity in kinetic resolution of a primary alcohol through lipase-catalyzed transesterification by using a chiral acyl donor"Tetrahed

Keiji Hirose、Hiroyuki Naka、Masashi Yano、Sozaburo Ohashi、Koichiro Naemura 和 Yoshito Tobe：“使用手性酰基供体通过脂肪酶催化的酯交换反应提高伯醇动力学拆分的对映选择性”

Hirose K.: "A practical guide for the determination of binding constants"J. Incl. Phenom. and Macrocyclic Chem.. 39. 193-209 (2001)

Hirose K.：“测定结合常数的实用指南”J.