Syntheses of Highly Functionalized Hosts Having Both Metal Coordination and Hydrogen Bonding Sites and Analysis of the Molecular Recognition Mechanisms.

为了理解酶的分子识别机制，合成了同时具有金属配位和氢键结合位点的人工宿主分子。(1)含萘酚环的Salen金属配合物与氨基酸衍生物的结合研究通过NMR滴定实验发现，镍配合物与组氨酸二甲酯的结合较弱，咪唑环在这种结合中起重要作用。钴配合物与苯丙氨酸甲酯通过紫外光谱的变化而相互作用。缔合常数和主客体结构正在研究中。(2)含酚环的Salen金属配合物与胺的结合研究发现，镍配合物与单胺和二胺分别以1：2和1：1的主客体比相互作用。通过NMR滴定研究获得的结合常数约为。10^3-10^4 M^<-1>。由于2，7-二氨基芴的结合常数最大，推测金属和中心酚都是结合位点。此外，salen锰配合物具有催化烯烃环氧化的活性。

To understand the mechanism of molecular recognition in enzymes, artificial host molecules having both metal coordination and hydrogen bonding sites were synthesized.(1) Binding study of salen-metal complexes having naphthol ring with amino acid derivatives.From the NMR titration experiments, it was found that the nickel complex weakly binds with histidine dimethyl ester and the imidazole ring is played a important role in this binding. The cobalt complex is interacted with phenylalanine methyl ester by the fact of the UV spectral changes. The association constant and the host-guest structures are now under investigation.(2) Binding study of salen-metal complexes having phenol rings with amines.The nickel complex was found to interact with mono- and diamines by the 1 : 2 and 1 : 1 host-guest ratios, respectively. The binding constants obtained by the NMR titration studies were ca. 10^3-10^4 M^<-1>. Since 2, 7- diaminofluorene shows the largest association constant, both the metal and the central phenol are presumed to be the binding sites. Furthermore the salen manganese complex was shown to have a catalytic activity of olefin epoxidation.