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REACTION CONTROL OF BIOLOGICALLY RELATED COMPOUNDS (SUGARS, AMINO ACIDS AND THEIR ANALOGOUS) BY HIGHLY FUNCTIONALIZED METAL COMPLEXES

高功能化金属络合物对生物相关化合物（糖、氨基酸及其类似物）的反应控制

基本信息

批准号：
63470035
负责人：
YANO Shigenobu
金额：
$ 3.26万
依托单位：
NARA WOMEN'S UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

项目摘要

Effective synthetic procedures, transformations and development of methods of molecular recognition for sugars and amino acids or their derivatives are highly desirable in the field of medicinal chemistry, biochemistry, and industry. In our laboratory, we have extensively studied the synthesis and characterization of nickel(II) complexes containing N-glycosides derived from the reaction of monosaccharides and diamines as a class of substitution labile. Metal complexes are divided into two classes such as substitution inert and substitution labile on the basis of their chemical properties. Therefore, it is interesting to examine these two types of complexes in order to elucidate the interaction of sugars with metals.Form this point of view, in this project we firstly have studied on the typically substitution inert cobalt(III) complexes containing an N-glycoside derived from ethylenediamine and aldoses. During our investigations on sugar complexes, we previously found that aldoses are epimerized at C-2 in a very short time by a nickel (II) N,N,N'-Me_3en complex, [Ni(H_2O)_2(N,N,N'-Me_3en)_2]Cl_2 (N,N,N'-Me_3 en = 1-(di methylamino)-2-(methylamino)ethane), which was accompanied by a stereoselective complexation of some mannose-type epimers. And under mild conditions, these aldoses were smoothly recovered from complexes by treatment with a slightly acidic aqueous solution. We applied the newly discovered sugar transformation reaction using [Ni(H_2O)_2 (N,N,N'-Me_3en)_2]^<2+> applied to the synthesis of the disaccharides having the mannoge reducing terminal from their C-2 reducing terminal epimers which are abundant in nature and are very difficult to synthesize by organic procedures. Next we investigated the fundamental study concerning molecular recognition by an aminopoly-carboxylate cobalt(III) complex. Finally we examined the reaction of an amino acid precursor with a cobalt(III)-polyamine complex.

在药物化学、生物化学和工业领域中，糖和氨基酸或其衍生物的有效合成方法、分子识别方法的转化和发展是非常必要的。在本实验室中，我们广泛地研究了单糖与二胺反应生成的N-糖苷镍(II)配合物的合成与表征。金属络合物按化学性质可分为惰性取代和不稳定取代两大类。因此，研究这两种类型的配合物以阐明糖与金属的相互作用是很有意义的。从这一角度出发，本项目首先研究了典型的取代惰性钴(III)配合物，其中含有乙二胺和醛糖衍生的N-糖苷。在对糖类络合物的研究中，我们发现在很短的时间内，醛类化合物会被镍(II)N，N，N‘-Me_3en络合物[Ni(H_2O)_2(N，N，N’-Me_3en)_2]Cl_2(N，N，N‘-Me_3en=1-(二甲氨基)-2-(甲氨基)乙烷)异构化，并伴随着一些甘露糖型差向异构体的立体选择性络合。在温和的条件下，用弱酸性水溶液处理，这些醛糖可以顺利地从络合物中回收。我们将新发现的[Ni(H_2O)_2(N，N，N‘-Me_3en)_2]和lt；2+的糖转化反应应用于由C-2还原末端异构体合成具有甘露还原端的二糖。接下来，我们研究了氨基多酸-羧酸钴(III)络合物分子识别的基础研究。最后，我们研究了氨基酸前体与钴(III)-多胺络合物的反应。