Hybrid Synthesis of Optically Active Receptors Possessing Chiral Recognition Ability

具有手性识别能力的光学活性受体的杂化合成

• 批准号: 04453024
• 负责人: NAEMURA Koichiro
• 金额: $ 4.67万
• 依托单位: Osaka 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: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453024/
• 关键词: Chiral crown ether; Chiralrecognition; Hybrid synthesis; Lipase; Active site model; 酵素的加水分解; 酵素による光学分割; 光学活性クラウンエーテル; アミノ酸の光学分割; 不斉識別機能を持つレセプター

Some optically active crown ethers possessing chiral recognition ability were synthesized by using synthetic chiral building blocks as cis-1-phenylcyclohexane-1,2-diol which were prepared by the enzymatic optical resolution. Chiral recognition behavior of these crown ethers toward chiral amines was evaluated and, on the basis of the results, the mechanism of the chiral recognition behavior was examined. meso-Crown ehters which have diastereotopic faces and form diastereoisomeric complexes were prepared by using the racemic cyclohexane derivative as a steric barrier. Diastereotopic face selectivity in complexation of meso-crown ethers with achiral amines was examined.In order to obtain further informations on the mechanism of the chiral recognition, chiral crown ethers which possess the more pre-organized binding cavity were prepared and their chiral recognition abilities were studied in 1994.Our research results of the chiral recognition and diastereotopic face selectivity in complexation obtained in the three years would provide helpful informations to assist in the design of more elaborate and structured synthetic receptors.Further, stereoselectivity of lipase YS-catalyzed hydrolysis and transesterification was examined and the active site model for this lipase to identify which enantiomer of a substrate reacts faster in the reaction was reported. In 1994, stereoselectivity of transesterification mediated by lipase QL was studied and the active site model for lipase QL was also proposed. These active site models make the reactions mediated by the lipases more usefull for stereoselective organic synthesis.

以酶解法合成的顺-1-苯基环己烷-1,2-二醇为手性结构单元，合成了具有手性识别能力的旋光性冠醚。评价了这些冠醚对手性胺的手性识别行为，并在此基础上探讨了其手性识别行为的机理。以外消旋环己烷衍生物为位阻，制备了具有非对映面并形成非对映异构体配合物的中冠醚。研究了中冠醚与非手性胺络合反应的非对映面选择性。为了进一步了解手性识别的机理，1994年制备了具有较强预组织结合腔的手性冠醚，并对其手性识别能力进行了研究。我们三年来在络合中的手性识别和非对映面选择性方面的研究成果将为设计更精细和结构化的合成受体提供有益的信息。此外，研究了脂肪酶ys催化水解和酯交换反应的立体选择性，并报道了该脂肪酶的活性位点模型，以确定底物的哪个对映体在反应中反应更快。1994年，研究了脂肪酶QL介导的酯交换立体选择性，并提出了脂肪酶QL的活性位点模型。这些活性位点模型使脂肪酶介导的反应在立体选择性有机合成中更加有用。

项目成果

Koichiro Naemura: "Enzyme-catalysed Asymmetric Hydrolysis and Enantioselective Hydrolysis of Acetates of Spiro Compounds with Axial Chirality" J.Chem.Research(S). 174-175 (1992)

Koichiro Naemura：“具有轴向手性的螺化合物乙酸酯的酶催化不对称水解和对映选择性水解”J.Chem.Research(S)。

Koichiro Naemura: "The Synthesis of Azophenolic Crown Ethers of Cs Symmetry incorporating cis-1-Phenylcyclohexane-1,2-diol Residues as a Steric Barrier and Diastereotopi Face Selectivity in Complexation of Amines by their Diastereotopic Faces" J.Chem.Soc.

Koichiro Naemura：“结合顺式-1-苯基环己烷-1,2-二醇残基作为空间屏障的 Cs 对称偶氮酚冠醚的合成以及胺通过非对映面络合时的非对映面选择性”J.Chem.Soc。

Koichiro Naemure: "大環状化合物を用いるアミノ酸の光学分割" ぶんせき. 6. 414-421 (1993)

Koichiro Naemure：“使用大环化合物光学拆分氨基酸”Bunseki 6. 414-421 (1993)。

Koichiro NAEMURA et al.: "Preparation and Enantiomer Recognition Behaviour of Crown Ethers containing cis-1-Phenyl-cyclohexane-1,2-diol and trans-1,2-Diphenylcyclohexane-1,2-diol as a Chiral Subunit" J.Chem.Soc.Perkin Trans.1. (1993)

Koichiro NAEMURA 等人：“含有顺式 1-苯基-环己烷-1,2-二醇和反式-1,2-二苯基环己烷-1,2-二醇作为手性亚基的冠醚的制备和对映体识别行为”J.

Koichiro Naemura: "Resolution of Diols of Bicyclo〔2.2.1〕heptane,Bicyclo〔2.2.2〕octane and Bicyclo-〔3.2.1〕octane by Enzymatic Hydrolysis and their Absolute Configurations" J.Chem.Soc.Rerkin Trans.1. 2337-2343 (1992)

Koichiro Naemura：“通过酶水解解析双环[2.2.1]庚烷、双环[2.2.2]辛烷和双环[3.2.1]辛烷二醇及其绝对构型”J.Chem.Soc.Rerkin Trans.1 .2337-2343 (1992)