Chiral Recognition and Stereoselective Catalysis of Chiral Footprint Cavities.

手性足迹空腔的手性识别和立体选择性催化。

• 批准号: 06680560
• 负责人: MORIHARA Kensaku
• 金额: $ 1.47万
• 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 (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06680560/
• 关键词: Molecular Imprinting; Footprint Cavities; Chiral Recognition; Autocatalysis; Asymmetric Amplification; エナンチオ選択

This research project concerned the "footprint catalysis" study ; it was aimed its application to (1) enantioselective catalysis and (2) autocatalytic assymetric amplification. The footprint catalysis means an artificial catalytic antibody study, that is, a method for tailor-made catalyst design based on specific catalytic action of footprint cavities imprinted on a silica gel surface by the author's molecular imprinting with a proper template. Results : (1) The chirally imprinted footprint cavities using L-proline-hydantoin template showed highly enantioselective catalytic activities in nucleophilic cleavage of hydantoin rings of L-proline-, 5-methyl, and 5-phenyl-hydantoins. The cavities transformed L-isomers nearly 20 times effectively than D-isomers. An unique mechanism was proposed for these high enantioselectivities based on asymmetric face recognition of hydantoin rings.(2) Footprint cavities imprinted with meso- (Z-Ala) _2NH catalized transacylation of LL,DD,and racemic isomers of (Z-Ala)_2O,respectively. In the catalysis, Z-L-alaninate, and Z-D-alaninate, one of the reaction product, stereoselectively showed competitive inhibition. It implied that cavities imprinted with meso- (Z-Ala) _2NH stereoselectively catalize meso- (Z-Ala) _2O under the presence of 2-D-alaninate to proceed transacylation of Z-D-alaninate, the latter of which promote the stereo-selective catalysis. Thus a potential autocatalytic asymmetric amplification was kinetically suggested to occur by the feed back mechanism.

该研究项目涉及“足迹催化”研究。它的目的是将其应用于（1）对映选择性催化和（2）自催化囊泡扩增。足迹催化是指人造催化抗体研究，即一种基于作者用适当模板的分子烙印在硅胶表面上印在硅胶表面上的足迹腔的特定催化作用的定制催化剂设计的方法。结果：（1）使用L-丙酸酯模板的手性印迹的足迹腔显示在L-丙啉，5-甲基和5-苯基羟基丁烷的Hydantoin环的亲核性裂解中显示出高度的对映选择性催化活性。这些空腔比D-Isomers有效地改变了L-Isomers的20倍。基于Hydantoin环的不对称面部识别，为这些高对映选择性提出了一种独特的机制。（2）分别以（Z-Ala）_2O的LL，DD和Racemicals的Meso-（Z-ALA）_2NH归化的跨跨囊化的足迹腔。在催化剂中，反应产物之一的Z-L-丙酸酯和Z-D-丙氨酸是立体选择性表现出竞争性抑制作用的。这暗示着印有介质（z-ala）_2NH立体选择性地将中的腔（z-ala）_2O催化的腔体在2-D-丙烷酸的存在下催化中_2o，以继续Z-D-丙酸酯的transaciation进行transaciation，其中后一种促进了立体选择性选择性催化催化催化性。因此，通过馈回机制进行了动力学提出潜在的自催化不对称扩增。