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。

基本信息

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

项目摘要

(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)糖类选择性合成反应的进展。通过与间苯二酚醛环四聚体氢键络合溶解在四氯化碳中的核糖，发现其与甲醇进行甲基化，高度立体选择性地生成甲基呋喃核糖苷。(2)通过氢键对糖进行分子识别。间苯二酚醛环四聚体被发现可以区分糖的轻微结构差异氢键固定。因此可以区分果糖与葡萄糖以及甲基吡喃葡萄糖苷的α端基异构体与β端基异构体。(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表现出具有裂棉效应的圆二色性。棉花效应的迹象可能与糖的构象相关，枯萎C1或1C。(4)新型糖粘合剂的开发。制备了基于八氮杂大环的新型大环化合物。它由八个具有极性羟基的长烷基链官能化。人们发现氯仿中的这种大环可以从水中提取各种极性物质，包括糖。不仅单糖（葡萄糖和果糖）而且二糖都可以通过这种方式溶解。因此，这项工作基于非极性有机介质中的特定主客体相互作用，打开了糖化学全新领域的大门。这个概念可以应用于糖的合成、分析、结构和有机方面。