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

具有金属配位和氢键位点的高功能化主体的合成以及分子识别机制的分析。

• 批准号: 09640637
• 负责人: USUI Shuji
• 金额: $ 1.92万
• 依托单位: Hiroshima International University (1998)Hiroshima University (1997)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640637/
• 关键词: metal coordination; hydrogen bonding; functionalized host; molecular recognition; amino acid; salen complex; association; chiral recognition; サレンニッゲル錯体

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.

为了了解酶的分子识别机制，合成了同时具有金属配位和氢键位点的人工宿主分子。（1）具有萘酚环的salen-金属配合物与氨基酸衍生物的结合研究。从NMR滴定实验发现，镍配合物与组氨酸二甲酯的结合较弱，而咪唑环在其中起重要作用。 这个绑定。钴配合物通过紫外光谱变化与苯丙氨酸甲酯相互作用。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。发现镍配合物分别以1:2和1:1的主客体比例与单胺和二胺相互作用。通过 NMR 滴定研究获得的结合常数约为。 10^3-10^4M^<-1>。由于 2, 7-二氨基芴显示出最大的缔合常数，因此推测金属和中心酚都是结合位点。此外，萨伦锰配合物显示出具有烯烃环氧化的催化活性。

项目成果

Hirotaka Kurabayashi: "Conformational Analysis of Dioxa[2.2]orthocyclophanes" Tetrahedron. 54-44. 13495-13504 (1998)

Hirotaka Kurabayashi：“二氧杂[2.2]正环芳烷的构象分析”四面体。

Yoshimasa Fukazawa: "Conformational Analysis by Chemical Shift Simulation" Journal of Synthetic Organic Chemistry,Japan. 55・12. 1124-1133 (1997)

深泽芳正：“通过化学位移模拟进行构象分析”，《合成有机化学》，日本，1124-1133（1997）。

Yoshimasa Fukuzawa: "Conformational Analysis by Chemical Shift Simulation" Journal of Synthetic Organic Chemistry, Japan. 55・12. 1124-1133 (1997)

福泽义正：“化学位移模拟的构象分析”，日本合成有机化学杂志 55・123（1997 年）。

Yoshimasa Fukazawa: "Conformational Analysis by Chemical Shift Simulation" J.Synth.Org.Chem., Japan. 55-12. 1124-1133 (1997)

Yoshimasa Fukazawa：“通过化学位移模拟进行构象分析”J.Synth.Org.Chem.，日本。

Hirotaka Kurebayashi: "Conformational Analysis of Dioxa[2.2]orthocyclophanes" Tetrahedron. 54・44. 13495-13504 (1998)

Hirotaka Kurebayashi：“二氧杂环己烷[2.2]正环芳烃的构象分析”四面体 54・44（1998）。