Asymmetric Syntheses by Use of Intercalation of Multi-nuclear Chiral Metal Complexes into a Clay

利用多核手性金属配合物插层到粘土中的不对称合成

• 批准号: 05453048
• 负责人: YAMAGISHI Akihiko
• 金额: $ 3.39万
• 依托单位: Hokkaido 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: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453048/
• 关键词: Clay minerals; Asymmetric Catalysis; Induced CD; Electric dichroism; 不斉場; 多核錯体

The purpose of the present project is to develop of a new catalytic system for asymmetric syntheses by use of clay minerals. Our approach is to synthesize an intercalation compound of a clay with optically active metal complexes. The chiral metal complexes are expected to form a chiral reaction space within the clay layrs. If the metal complexes are capable to catalyze some reactions (e.g.oxidation, reduction, hydrogenation etc), they will achieve asymmetric syntheses with high efficiency.As a result, we have established the following reaction systems involving a clay. Two kinds of metal complexes were coadsorbed by a colloidally dispersed clay ; [Fe (terpy) ] ^<3+> terpy=2,2', 2''- terpyridyl) and [Ni (phen) _3]^<2+> (phen=1,10-phenanthroline). The Fe complex is capable of oxidizing an organic substance such as ascorbic acid or cystein, but it has no optical activity. The Ni complex has no redox properties but it is chiral due to the helical nature of three phenanthroline ligands. It was expected that the oxidation by the Fe complex proceeded under the chiral circumstances of the Ni complex when these two kinds of complexes were on the same clay surface. This was realized by comparing the oxidation rates of D- or L-cystein in the presence of a colloidally dispersed clay absorbing [Fe (terpy) ] ^<3+> and DELTA- [Ni (phen) _3] ^<2+>. L-Cystein was found to be oxidized at the higher rate than D-cystein, showing the stereoselectivity in the reaction.The structures of the present clay catalysis have been investigated with various spectroscopic methods : the measurements of induced CD,the electric dichroism spectra and the observations with atomic force microscopy.

本项目的目的是通过使用粘土矿物来开发一种新的催化系统，用于不对称合成。我们的方法是合成具有光学活性金属络合物的粘土的插入化合物。预计手性金属络合物将在粘土层中形成手性反应空间。如果金属络合物能够催化某些反应（例如氧化，还原，氢化等），则它们将以高效率实现不对称的合成。因此，我们已经建立了以下涉及粘土的反应系统。两种金属络合物通过胶体分散的粘土共同吸附。 [fe（terpy）] ^<3+> terpy = 2,2'，2'' - terpyridyl）和[ni（ni（phen）_3] ^<2+>（pel = 1,10-苯烷氨基氨酸）。 FE配合物能够氧化有机物质，例如抗坏血酸或西斯坦，但没有光学活性。 Ni复合物没有氧化还原特性，但由于三种妥变体配体的螺旋性质，它是手性的。可以预期，当这两种复合物在同一粘土表面时，在Ni复合物的手性情况下进行了FE复合物的氧化。通过比较在存在胶体分散的粘土[Fe（terpy）] ^<3+>和delta-- [ni（phan）_3] _3] ^<2+>的情况下，在存在胶体分散的粘土[Fe（terpy）] ^<3+>上的氧化速率来实现的。发现L-Cystein以比D-Cystein更高的速率被氧化，显示了反应中的立体选择性。已经通过各种光谱方法研究了本粘土催化的结构：诱导的CD的测量值：电二二核酸谱，与原子力显微镜观察。

项目成果

Y.Ken, K.Shimazu & A.Yamagishi: "Mass Transport on a Clay Modified Electrode as studied by Quartz Crystal Microbalance Method" Chem.Lett.161-161 (1995)

Y.Ken, K.岛津

山岸晧彦、堀田裕司: "粘土薄膜の電極修飾剤への応用" 粘土科学. 33. 233-245 (1994)

Akihiko Yamagishi，Yuji Hotta：“粘土薄膜在电极改性剂中的应用”Clay Science 33. 233-245 (1994)。

A.Yamagishi, H.Sato: "Molecular Recognition on a Clay Surface : Theoretical Approrch" Hyomen. 31. 375-387 (1993)

A.Yamagishi、H.Sato：“粘土表面的分子识别：理论方法”Hyomen。

姚建,嶋津克明,山岸晧彦: "Mass transport on a clay modified electrode as studied by quartz crystal microbalance method" Chemistry Letters. 161-161 (1995)

Ken Yao、Katsuaki Shimazu、Akihiko Yamagishi：“通过石英晶体微天平方法研究粘土改性电极上的质量传输”化学快报 161-161 (1995)。

A.Yamagishi, M.Takahashi & M.Taniguchi: "Electin Dichroism Studies on Adsorption of [Ru (DMOPY) _3] ^<2+> by a colloidal Clay" J.Phys.Chem.98. 7555-7561 (1994)

山岸先生、高桥先生