Nonenymic Sugar Transformation promoted by Metal Complexes

金属配合物促进非酶糖转化

• 批准号: 60470084
• 负责人: YANO SHIGENOBU
• 金额: $ 3.26万
• 依托单位: Tokyo University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60470084/
• 关键词: Sugar Complex; Sugar Transformation; EXAFS; X線結晶構造解析

Much attention has recently been focused on rare naturally occurring sugars, with the elucidation of the biological functions of carbohydrates contained in glycoprotains, glycolipids, nucleic acids, and antibiotics. It is thus desirable to develop a methods whereby metal complexes promote transformations of sugars and stereoselective uptake of sugars. During a significant part of study to elucidate sugar-transition-metal interactions, an unprecedented binuclear nickel- (II) complex containing two types of N-glycosides formed from N,N'-dimethyl- ethylenediamine and D-mannose(DMna) was synthesized, and its structure was determined by X-ray crystallography. The metal center is a binuclear nickel complex with a bridbing mannose sugar residue. The bridging sugar ring takes the unusual furanose form. When D-glucose was used as a starting sugar instead of D- mannose, a nickel(II) complex was surprisingly obtained although its yield was very low. Prompted by this knowledge, we chose N,N,N'-trimethylethylenediamine (tmen) as the diamine component, which has one reaction point (secondary amino group) in the molecule. We have found that aldoses are rapidly epimerized at C- 2 in the presence of [Ni(H_2O)_2(tmen)_2]Cl_2 and, of the two C-2 epimers, nickel(II) ions form complexes with only the mannose-type epimers stereoselectively. The EXAFS study suggested that the Key to the stereoselective complexation of mannose type epimers lies in the bridging part of the furanoside residue which seems to have a strong affinity for-nickel(II) ions. The 13 C.NMR. study-of the Ni^<2+>- diamine-[1-^3C]-D-glucose system reveals that a novel stereospecific rearrangement of the carbon skleton, the exchange of C-1 and C-2 atoms by inversion of the C-1-C-2 aldose fragment, is involved in this reaction. The EXAFS study indicated that the reactive complex is mono nuvclear. From these observations obtained we proposed a plausible mechanism for the epimerization in the Ni2+- diamine-aldose system.

近年来，随着糖蛋白、糖脂、核酸和抗生素中碳水化合物的生物学功能的阐明，大量的注意力集中在稀有的天然糖上。因此，需要开发一种方法，由此金属络合物促进糖的转化和糖的立体选择性摄取。在阐明糖-过渡金属相互作用的研究中，合成了一种前所未有的双核镍（II）配合物，其包含由N，N '-二甲基乙二胺和D-甘露糖（DMNa）形成的两种类型的N-糖苷，并通过X射线晶体学确定了其结构。金属中心是一个双核镍配合物与桥甘露糖残基。桥糖环采取不寻常的呋喃糖形式。当使用D-葡萄糖代替D-甘露糖作为起始糖时，令人惊讶地获得镍（II）络合物，尽管其产率非常低。基于这一认识，我们选择N，N，N '-三甲基乙二胺（tmen）作为二胺组分，其在分子中具有一个反应点（仲氨基）。我们发现，在[Ni（H_2O）_2（tmen）_2]Cl_2存在下，醛糖在C- 2上迅速发生差向异构化，并且在这两种C-2差向异构体中，镍离子只与甘露糖型差向异构体立体选择性地形成络合物。EXAFS研究表明，甘露糖型差向异构体立体选择性络合的关键在于呋喃糖苷残基的桥接部分，这似乎对镍（II）离子具有很强的亲和力。13 C. NMR。对Ni^<2+>-二胺-[1-^3C]-D-葡萄糖体系的研究表明，该反应涉及一种新的碳骨架的立体专一性重排，即通过C-1-C-2醛糖片段的反转进行的C-1和C-2原子的交换。EXAFS研究表明，反应性络合物是单核的。从这些观察结果中，我们提出了一个合理的机制差向异构化的Ni 2 +-二胺-醛糖系统。

项目成果

T. Tanase: "Reaction of [Ni(H_2O)_2(N,N'-Me_2-en)_2]^<2+> with Carbohydrates. Synthesis and Characterization of a Novel u-Mannofuranoside Binuclear Nickel(2) Complex Containing N-Glycosides" 26. 3134-3139 (1987)

T. Tanase：“[Ni(H_2O)_2(N,N-Me_2-en)_2]^<2> 与碳水化合物的反应。含有 N- 的新型 u-甘露糖苷双核镍 (2) 复合物的合成和表征

棚瀬知明: J. Chem. Sac., Chem. Commun.659-661 (1987)

田濑智明：J. Chem.，Chem.659-661 (1987)

棚瀬知明: 東京大学工学部総合試験所強力X線実験室レポート. 3. 11-17 (1986)

Tomoaki Tanase：东京大学工程学院高强度 X 射线实验室报告，3. 11-17 (1986)。

棚瀬知明: Inorg. Chem.26. 3134-3139 (1987)

田濑智明：Inorg.26。

T. Tanase: "Reaction of Metal Complexes with Carbohydrates. Synthesis and Characterization of an Unprecedented u-Mannofuranoside Binuclear Nickel(2) Complexes Containing N-Glycosides" J. Chem. Soc., Chem. Conmun.1562-1564 (1985)

T. Tanase：“金属配合物与碳水化合物的反应。前所未有的含有 N-糖苷的 u-呋喃甘露糖苷双核镍 (2) 配合物的合成和表征”J. Chem。