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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.

用多核核磁共振等方法对几种高选择性有机反应的反应性络合物的溶液结构进行了详细的研究，得到了以下新的结果：1.膜电位变化的反应性络合物在以杯[6]芳烃六酯为基础的聚氯乙烯基质液膜上观察到的膜电位的选择性变化是基于空腔包裹体对非极性部分的区分。2.合成的一系列吲哚内酰胺类和苯内酰胺类新型模型化合物的溶液结构进行了详细的1H-核磁共振研究揭示了它们的活性构象为扭曲构象。3.锂的不对称反应络合物详细的~6Li和~1t；15&gt；N-核磁共振研究表明，在手性锂酰胺催化的不对称去质子反应中，导致高选择性的络合物是它与LiCl1：1的混合聚集体。4.催化不对称C-C键形成的反应络合物详细的1H-和^&lt；31&gt；P-核磁共振研究揭示了手性BINAP-Pd络合物的溶液结构，导致了催化不对称Heck和Aldol反应的高选择性。5.用于仿生催化氧化的活性络合物对未反应烷烃和芳香族化合物的催化氧化效率被证明是[Ru^^&lt；(POR)(X)(O)]^+(X=氯或溴)。