Application of Weak Coordination Concerning Calcium-Multidentate Ligand Complexes

钙多齿配体配合物弱配位的应用

• 批准号: 62470089
• 负责人: YOSHIKAWA Sadao
• 金额: $ 4.22万
• 依托单位: Keio 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: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-62470089/
• 关键词: Aldohexose; Epimerization; Ethylenediamine; Calcium; Monoamine; Glucose; モノアミン; ニッケル; エピメリ化; ケトース; 異性化糖

The development of methods whereby metals promote transformation of sugars is of considerable interest.We have recently reported the novel epimerization of aldoses promoted by the combination of Nickel and diamines, which proceeds rapidly under the mild basic condition.This time, various kinds of N-alkyl substituted ethylenediamine derivatives were prepared to study the effects of ligand on the epimerization. The introduction of more hydrophobic long alkyl groups at nitrogen atom affects the amphibility of the complex which plays an important role in the reaction.Among the ligands, N,N'-dialkylethylenediamine showed the most active ability for C-2 epimerization of glucose and mannose, which attained equilibrium in a few minutes under methanol reflux. The equilibrium points between C-2 epimer could be moved to glucose side by using the longer alkyl chain.The ^<13>C NMR studies of Nickel-diamine system using ^<13>C enriched D-glucose revealed that C-2 epimerization involves the novel sterospecific rearrangement of carbon skelton.Moreover, epimerization of aldoses were examined using calcium ions. The characteristics of calcium ions were the effectiveness of mono amine in contrast with the fact that no C-2 epimerization was observed in the Ni^<2+>- monoamine system.

利用金属促进糖转化的方法的发展引起了相当大的兴趣。我们最近报道了镍与二胺结合促进醛糖的新型外聚反应，该反应在温和的碱性条件下进行迅速。本次制备了各种n -烷基取代乙二胺衍生物，研究配体对外映反应的影响。在氮原子上引入较多疏水长烷基影响配合物的亲和性，对反应起重要作用。配体中，N，N′-二烷基乙二胺对葡萄糖和甘露糖的C-2外映反应最活跃，在甲醇回流下几分钟即可达到平衡。利用较长的烷基链可以将C-2表聚体的平衡点移到葡萄糖侧。用富集了^<13>C的d -葡萄糖对镍-二胺体系进行了^<13>C核磁共振研究，发现C-2外映化涉及碳骨架的新型立体定向重排。此外，还用钙离子考察了醛糖的外聚作用。在Ni^<2+>-单胺体系中，没有观察到C-2外聚，而钙离子的特征是单胺的有效性。

项目成果

K.Ishida: Inorg.Chem.25. 3552-54 (1988)

K.Ishida：Inorg.Chem.25。

K. Ishida: "Synthesis and Characterization of Substitution Inert Cobalt(III) Complexes Containing an N-Glcoside Derived from Ethylenediamine and a monosaccharide." Inorg. Chem.25. 3552-3554 (1988)

K. Ishida：“含有乙二胺和单糖衍生的 N-糖苷的取代惰性钴 (III) 配合物的合成和表征。”

T.Tanase;K.Kurihara;S.Yano;K.Kobayashi;T.Sakurai;S.Yoshikawa;M.Hidai: Inorg.Chem.26. 3134-39 (1987)

T.Tanase;K.Kurihara;S.Yano;K.Kobayashi;T.Sakurai;S.Yoshikawa;M.Hidai：Inorg.Chem.26。

K.Ishida.: Inorg.Chem.25. 3552-4 (1988)

K.Ishida.：Inorg.Chem.25。

T.Tanase;K.Kurihara;S.Yano;K.Kobayashi;T.Sakurai;S.Yoshikawa;M.Hidai: Inorg.Ghem. 26. 3134-3139 (1987)

T.Tanase;K.Kurihara;S.Yano;K.Kobayashi;T.Sakurai;S.Yoshikawa;M.Hidai：Inorg.Ghem。