Development of Selective Synthetic Reactions of Sugars Based on Their Complexation.

基于糖的络合选择性合成反应的发展。

• 批准号: 01470094
• 负责人: AOYAMA Yasuhiro
• 金额: $ 4.29万
• 依托单位: Nagaoka University of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470094/
• 关键词: sugars; hydrogen bonding; host-guest; molecular recognition; circular dichroism; 糖グリコシド; グリコシル化; ホスト-ゲスト

(1) Development of Selective Synthetic Reactions of Sugars.Ribose solubilized in carbon tetrachloride via hydrogen-bonding complexation with resorcinolaldehyde cyclotetramer was found to undergo methylation with methanol to give methyl betaribofuranoside highly stereoselectively.(2) Molecular Recognition of Sugars via Hydrogen-Bonding.Resorcinol-aldehyde cyclotetramer was found to discriminate slight structural differences in sugars in their hydrogen-bonding fixation. It was thus possible to differentiate fructose vs glucose and alpha anomer of methyl glucopyranoside from the beta anomer.(3) Determination of Sugar Conformation Based on Induced Circular Dichroism.The sugar complexes of resorcinol-aldehyde cyclotetramer exhibit circular dichroism with split Cotton effects. The signs of the Cotton effects could be correlated with the conformation of the sugar, wither C1 or 1C.(4) Development of a New Class of Sugar Binder.A new class of macrocycle based on an octaazamacrocycle was prepared. It was functionalized by eight long-alkyl chains having polar OH groups. This macrocycle in chloroform was found to extract various polar materials including sugars from water. Not only monosaccharides (glucose and fructose) but also disaccharides could be solubilized in this manner.This work thus opens the door to an entirely new field of sugar chemistry, based on apecific host-guest interactions in apolar organic media. This concept can be applied to the synthetic, analytical, structural, and organic aspects of the sugars.

(1)糖的选择性合成反应的发展：发现通过与间苯二酚醛环四聚体的氢键络合溶解在四氯化碳中的核糖与甲醇进行甲基化，高度立体选择性地得到甲基betaribofuranoside。(2)糖的氢键分子识别：间苯二酚-醛环四聚体被发现在糖的氢键固定中可以区分糖的微小结构差异。因此，可以区分果糖与葡萄糖以及甲基吡喃葡萄糖苷的α异头体与β异头体。(3)基于诱导圆二色性的糖构象测定间苯二酚-醛环四聚体的糖复合物显示具有裂棉效应的圆二色性。Cotton效应的信号可能与糖的构象，枯萎C1或1C相关。(4)一类新型糖粘合剂的研制制备了一类基于八氮杂大环的新型大环化合物。它被官能化的八个长的烷基链具有极性OH基团。发现氯仿中的这种大环可以从水中提取包括糖在内的各种极性物质。不仅单糖（葡萄糖和果糖），而且二糖也可以用这种方式溶解。这项工作因此打开了一扇全新的糖化学领域的大门，基于非极性有机介质中的特定主客体相互作用。这个概念可以应用于糖的合成、分析、结构和有机方面。

项目成果

Kenji Kobayashi: "Solubilization of Sugars in Apolar Organic Media via Microsolvation Effect." J.Am.Chem.Soc.

Kenji Kobayashi：“通过微溶剂化效应在非极性有机介质中溶解糖。”

Yasutaka Tanaka: "Highly Stereoselective Glycosidation of Ribose Solubilized in Apolar Organic Media via HostーGuest Complexation." Tetrahedron Lett.31. 6193-6196 (1990)

Yasutaka Tanaka：“通过主客体络合在非极性有机介质中溶解核糖的高度立体选择性糖苷化。”31 (1990)。

Y.Tanaka,C.Kahre,Y.Aoyama: "Direct Glycosidation of Ribose Bound with Resorcinol-Aldehyde Cyclotetramer in CCl4." Tetrahedron Lett.

Y.Tanaka、C.Kahre、Y.Aoyama：“在 CCl4 中与间苯二酚醛环四聚体结合的核糖的直接糖苷化。”

Yasuhiro Aoyama: "Molecular Recognition.5.Mlecular Recognition of Sugars via HydrogenーBonding Interaction with a Synthetic Polyhydroxy Macrocycle." J.Am.Chem.Soc.111. 5397-5404 (1989)

Yasuhiro Aoyama：“分子识别。5.通过与合成多羟基大环的氢键相互作用进行糖的分子识别。”J.Am.Chem.Soc.111（1989）。

Yasutaka Tanaka: "Selective Sugar Binding with a Synthetic Polyhydroxy Macrocycle. A Remarkable Selectivity for Fructose over Glucose." Chem. Lett.1905-1908 (1989)

Yasutaka Tanaka：“与合成多羟基大环选择性糖结合。果糖相对于葡萄糖具有显着的选择性。”