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.

本课题的目的是利用粘土矿物开发一种新的不对称合成催化体系。我们的方法是合成一种粘土与光学活性金属配合物的插层化合物。手性金属配合物有望在粘土层内形成手性反应空间。如果金属配合物能够催化某些反应（如氧化、还原、氢化等），它们将实现高效的不对称合成。因此，我们建立了以下涉及粘土的反应体系。两种金属配合物（[Fe（terpy）] ^<3+> terpy= 2，2 '，2“- terpyridyl）和[Ni（phen）_3]^<2+>（phen= 1，10-Phenanthroline）被胶体分散粘土共吸附。Fe络合物能够氧化有机物质如抗坏血酸或半胱氨酸，但它没有光学活性。镍配合物没有氧化还原性质，但它是手性的，由于三个菲咯啉配体的螺旋性质。当这两种配合物位于同一粘土表面时，预计Fe配合物的氧化是在Ni配合物的手性环境下进行的。这是通过比较D-或L-半胱氨酸在吸附[Fe（terpy）] ^<3+>和DELTA- [Ni（phen）_3] ^<2+>的胶体分散粘土存在下的氧化速率来实现的。发现L-半胱氨酸的氧化速率比D-半胱氨酸高，表明反应具有立体选择性。本文采用多种光谱方法研究了粘土催化剂的结构：诱导CD测量、电二色性光谱和原子力显微镜观察。

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)。

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, 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。

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