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

为了了解酶分子识别的机制，合成了同时具有金属配位和氢键位点的人工宿主分子。(1)含萘酚环的盐-金属配合物与氨基酸衍生物的结合研究。通过核磁共振滴定实验，发现镍配合物与组氨酸二甲酯弱结合，咪唑环在这种结合中起重要作用。钴配合物通过紫外光谱变化与苯丙氨酸甲酯相互作用。目前正在调查关联常数和主客结构。(2)含酚环的盐-金属配合物与胺的结合研究。镍配合物与单胺和二胺分别以1:1和1:1的主客体比例相互作用。通过核磁共振滴定研究得到的结合常数约为10^3-10^4 M^<-1>。由于2,7 -二氨基芴显示出最大的结合常数，因此推测金属和中心酚都是结合位点。此外，salen锰配合物还具有烯烃环氧化的催化活性。

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.