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Development of Sugar Transformation System Using New Complex Catalysis

利用新型复合催化开发糖转化系统

基本信息

批准号：
01850190
负责人：
YANO Shigenobu
金额：
$ 3.2万
依托单位：
Nara Women's University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental 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/grant/KAKENHI-PROJECT-01850190/
关键词：
Epimerization Sugar Transformation Sugar Alcohol Metal Complex 糖

项目摘要

Effective synthetic procedures for naturally rare carbohydrates and their derivatives are highly desirable in the field of industry. Form this point of view we have carried out the following investigations. We examined the C-2 epimerization of aldoses in methanol, by combinations of diamines, monoamines or aminoalcohols with some transition metal, alkaline earth metal and rare earth metal ions which have affinity for carbohydrates. Among the metal ions used, Ni^<2+>, Co^<2+> and Ca^<2+> proved to be effective. The Ca^<2+> -N-substituted monoamine system in particular has many advantage for practical use. The reaction mechanisms of these sugar transformation reactions have been clarified by nuclear magnetic resonance, electronic absorption, circular dichroism and EXAFS spectroscopies. We observed that stereselective uptake of mannose type of the epimeric aldoses by nickel (II) complexes of N-subsituted diamines. In order to elucidate the factor that caused the stereoselective uptake we carried out the EXAFS study. This EXAFS study suggested that the key to the stereoselctive complexation of mannose-type aldoses having some donor groups lies in the briding part of the mannofuranoside residue which seems to have a strong affinity for nickel (II) ions. New nickel (II) N-glycoside complexes were formed from tris (2-aminoethyl) amine with aldoses. The amine ligands act as effective anchors for the accumulation of three sugar molecules. The newly discovered sugar trans formation reaction using Ca^<2+>-diethylamine (DEA) system was applied to the synthesis of D-mannitol, which is useful as a dietary sweeteners, from naturally abundant D-glucose. Isomerization and C-2 epimerization of the starting D-glucose by Ca^<2+>-DEA system and subsequent hydrogenation by rany nickel catalyst gave D-mannitol and D-glucitol in moderato yield. This simple system of Ca^<2+>- monoamine system might have much potential from a industrial point of view.

天然稀有碳水化合物及其衍生物的有效合成方法在工业领域是非常需要的。从这个观点出发，我们进行了以下调查。通过二胺、单胺或氨基醇与一些对碳水化合物有亲和力的过渡金属、碱土金属和稀土金属离子的结合，研究了醛糖在甲醇中的C-2外映反应。所使用的金属离子中，Ni^<2+>, Co^<2+>和Ca^<2+>被证明是有效的。特别是Ca^<2+> - n取代单胺体系具有许多实际应用的优点。利用核磁共振、电子吸收、圆二色性和EXAFS光谱等方法对糖转化反应的机理进行了研究。我们观察到n -取代二胺的镍（II）配合物对甘露糖型外端醛糖的立体选择性摄取。为了阐明引起立体选择性摄取的因素，我们进行了EXAFS研究。这项EXAFS研究表明，具有一些供体基团的甘露糖型醛糖的立体选择性络合的关键在于甘露呋喃苷残基的桥接部分，该部分似乎对镍（II）离子具有很强的亲和力。三（2-氨基乙基）胺与醛糖形成新的镍（II） n -糖苷配合物。胺配体作为三个糖分子积累的有效锚定体。利用Ca^<2+>-二乙胺（DEA）体系，将新发现的糖转化反应应用于从天然丰富的d -葡萄糖中合成可作为膳食甜味剂的d -甘露醇。用Ca^<2+>-DEA体系对起始d -葡萄糖进行异构化和C-2外映，然后用多种镍催化剂加氢得到d -甘露醇和d -葡萄糖醇，产率中等。从工业角度来看，这种简单的Ca^<2+>-单胺体系可能具有很大的潜力。