Structural Studies on Reactive Complexes for Highly Selective Organic Reactions

本文用多核核磁共振等方法详细研究了几种高选择性有机反应的反应性配合物的溶液结构，得到了以下新结果：1.膜电位变化的反应性配合物用杯[6]芳烃六酯PVC基液膜对多巴胺及相关化合物进行了膜电位的选择性变化，已经通过1H-NMR显示基于通过空穴包含来区分非极性部分。2.用于促进癌症的反应性络合物对一系列吲哚内酰胺类和苯并内酰胺类的溶液结构的详细1H-NMR研究，所述吲哚内酰胺类和苯并内酰胺类是作为TPA型癌症促进剂teleocidin的新型模型化合物合成的，详细的^6Li-和<15>1H-NMR研究表明，在手性氨基锂介导的不对称去质子化反应中，导致高选择性的络合物是其1：4.用于催化不对称C-C键形成的反应性络合物详细的~ 1H-和~ 1H-NMR<31>研究揭示了手性BINAP-Pd络合物的溶液结构，导致催化不对称Heck和Aldol反应的高选择性。5.用于仿生催化氧化的反应性络合物用~ 1H-NMR等方法研究了卟啉配合物的结构，证明它是[Ru^<VI>（por）（X）（O）]^+（X=Cl或Br）。

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.