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

在药物化学、生物化学和工业领域，糖和氨基酸或其衍生物的有效合成程序、转化和分子识别方法的发展是非常需要的。在我们的实验室里，我们广泛地研究了含n -糖苷的镍（II）配合物的合成和表征，这些配合物是由单糖和二胺反应而成的，作为一类取代不稳定物。金属配合物根据其化学性质可分为取代惰性和取代不稳定两类。因此，为了阐明糖与金属的相互作用，研究这两种类型的配合物是很有趣的。从这个角度来看，在这个项目中，我们首先研究了典型的取代惰性钴（III）配合物，其中含有由乙二胺和醛糖衍生的n -糖苷。在糖配合物的研究中，我们发现醛糖在很短的时间内被镍（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）在C-2处外映，并伴有一些甘露糖型外映体的立体选择性络合。在温和条件下，这些醛糖通过微酸性水溶液处理从配合物中顺利回收。我们将新发现的[Ni(H_2O)_2 (N，N，N'-Me_3en)_2]^<2+>的糖转化反应应用于从其C-2还原末端外显体中合成具有锰还原末端的双糖，这些双糖在自然界中含量丰富，很难用有机方法合成。接下来，我们对氨基聚羧酸钴（III）配合物的分子识别进行了基础研究。最后，我们研究了氨基酸前体与钴(III)-多胺络合物的反应。

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.