Design of chemical Reactions based on the Crystal Structures

基于晶体结构的化学反应设计

基本信息

批准号：
60303027
负责人：
IWASAKI Fujiko
金额：
$ 3.14万
依托单位：
The University of Electro-Communications
依托单位国家：
日本
项目类别：
Grant-in-Aid for Co-operative Research (A)
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1987
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-60303027/
关键词：
Molecular Design X-ray Crystal Stuctures Chiral Reactins Surface Structures Inclusion Compounds Molecular Mechanics Solid-state Reactions 反応立体経路

项目摘要

Relationships between crystal structures and reaction mechanism were studied cooperatively by X-ray Crystallographers, organic chemists and physical chemists. Many interesting results were obtained about the molecular design and the control of chemical ractions by use of the crystalline field.1. Chiral host compounds effective for optical resolution were found and chiral photoreactions in crystalline inclusion complexes were controlled (Toda). Crystalline-state reaction and - photoisomerization of cobaloxime complexes were studied by X-ray analysis (Ohashi).2. Based on X-ray structure analysis selective inclusion phenomena of cyclodextrins and -binaphthol were demonstrated (Fujiwara). The crystal structure of the synthetic moldenite was studied by an X-ray method and a behavior of the adsorbed ethylene on mordenite was observed by IR spectra (Ito).3. Orientation of surface molecules and reactions were investigated by Penning ionization electron spectroscopy (Harada). The mechanism of the topotactic formation and structure change in polyphthalocyanine caused by iodine doping were observed directly by high-resolution electron microscopy (Kobayashi).4. The mechanism of polymerization induced by irradiation and the interaction of enzymes with thier substrates were studied on the bases of X-ray structure analysis (Kai). The molecular design for new metallic CT complexes, multi-stage redox system, and the structure analysis were carried out (Nakasuji). Based on the X-ray structure analysis reaction paths via hypervalent intermediates and inter- or intramolecular interactin in the hypervalent sulfur compounds were investigated (Iwasaki).5. Molecular design for natural products was carried out by use of molecular mechanics (Osawa). Quantum chemical interpretation of oxidation number and -electronic structure was made with ab initio molecular orbitals (Hosoya).

X射线晶体学家，有机化学家和物理化学家协同研究了晶体结构与反应机制之间的关系。关于分子设计和通过使用晶体场的控制获得了许多有趣的结果。1。发现有效的光学分辨率的手性宿主化合物，并控制了晶体包容络合物中的手性光反应（TODA）。通过X射线分析（OHASHI）。2。基于X射线结构分析，证明了环糊精和二硫醇的选择性包容现象（Fujiwara）。通过X射线方法研究了合成霉菌的晶体结构，并通过红外光谱（ITO）观察到吸附的乙烯对冬日纪的行为。3。通过笔离子化电子光谱（Harada）研究了表面分子和反应的方向。直接通过高分辨率电子显微镜（Kobayashi）直接观察到由碘掺杂引起的多苯丙氨酸引起的拓扑形成和结构变化的机制。4。在X射线结构分析（KAI）的基础上研究了由辐照引起的聚合和酶与THIR底物的相互作用的聚合机制。进行新的金属CT复合物，多阶段氧化还原系统和结构分析的分子设计（Nakasuji）。基于X射线结构分析反应路径通过高价值中间体和在高价值硫化合物中的分子间相互作用或分子内相互作用（IWASAKI）。5。天然产物的分子设计是通过使用分子力学（Osawa）进行的。氧化数和 - 电子结构的量子化学解释是用摘要分子轨道（Hosoya）制成的。