Structural Studies on Reactive Complexes for Highly Selective Organic Reactions

高选择性有机反应反应配合物的结构研究

基本信息

批准号：
06557117
负责人：
ODASHIMA Kazunori
金额：
$ 6.85万
依托单位：
University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1995
项目状态：
已结题

项目摘要

Solution structures of reactive complexes for several kinds of highly selective organic reactions have been investigated in detail by multinuclear NMR spectroscopy and other methods, and the following new results have been obtained.1.Reactive Complexes for Membrane Potential Changes Selective changes in membrane potential, observed for dopamine and related compounds by a PVC matrix liquid membrane based on calix [6] arene hexaester, have been shown by ^1H-NMR to be based on discrimination of nonpolar moieties by cavity inclusion.2.Reactive Complexes for Promotion of Cancer Detailed ^1H-NMR investigations on the solution structures of a series of indolactams and benzolactams, synthesized as a novel type of model compounds of TPA-type cancer promoter teleocidin, have revealed their active conformation to be the twist form.3.Reactive Complexes for Asymmetric Reaction of Lithium Enolates Detailed ^6Li-and ^<15>N-NMR investigations have revealed that the complex leading to high selectivities in asymmetric deprotonation mediated by chiral lithium amide is its 1 : 1 mixed aggregate with LiCl.4.Reactive Complexes for Catalytic Asymmetric C-C Bond Formation Detailed ^1H-and ^<31>P-NMR investigations have revealed the solution structures of chiral BINAP-Pd complexes leading to high selectivities of catalytic asymmetric Heck and aldol reactions.5.Reactive Complexes for Biomimetic Catalyic Oxidation The complex leading to the high efficiencies of catalytic oxidation by Ru-porphyrin complex for unreactive alkanes and aromatic compounds has been shown to be [Ru^<VI> (por) (X) (O) ]^+ (X=Cl or Br) by ^1H-NMR and other methods.

通过多核NMR光谱和其他方法详细研究了多种高度选择性有机反应的反应性复合物的溶液结构，并获得了以下新结果。1。膜的反应性复合物，用于膜的潜在变化膜的选择性变化，膜的潜在变化是对多巴胺和液体膜的相关化合物的观察到的[6]，这是对两种异型的含量的观察到的[6]。 ^1H-NMR是基于通过腔包含对非极性部分的歧视。2。促进癌症的反应性复合物，详细研究 ^1H-NMR对一系列indolactams and Benzolactams的溶液结构进行了研究，被合成为TPA-type cancer cancer telecter的新型化合物的新型模型，以揭示其动态蛋白质，并揭示了他们的活跃蛋白，并揭示了他们的活跃蛋白。锂的不对称反应的复合物富含详细的 ^6li-and ^<15> n-nMR研究表明，通过手性锂酰胺介导的非对称质子化介导的高选择性的复合物是其1：1的1：1是其1：1的载体均匀骨料。手性BINAP-PD复合物的结构，导致催化不对称的Heck和Aldol反应的高选择性。5.仿生催化氧化的反应性复合物，导致ru-porporphyrin复合物的催化氧化效率的复合物，是对无抗烷烃和Arkanes的复合型复合物和Arkanes和Arkanes的复合效应的，已显示（x） ] ^+（x = cl或br）通过 ^1H-NMR和其他方法。