Design of the Molecules Bearing Specific Stereochemistry and Its Application to the Development of New Reactions

具有特定立体化学的分子设计及其在新反应开发中的应用

• 批准号: 02453141
• 负责人: NAGAO Yoshimitsu
• 金额: $ 2.69万
• 依托单位: The University of Tokushima
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-02453141/
• 关键词: Conformational Analysis; Dynamic ^1H- and ^<13>C-NMR; X-ray Analysis; Axial Conformer; Cyclohexanone; Thiane; Bent Conformation; Sigmoid Conformation; アキシアルコンホ-マ; チアン; チアンー1ーオキシド; チアンー1,1ージオキシド; ジヒドロチイン; 軌道相互作用; 機能性分子; 屈折型コンホ-ション

We are extensively developing a new system in which stereochemistry and reaction of the unique molecule can be regulated under the electronic control.Conformational analysis of various six-membered ring compounds possessing alkoxy and silyloxy substituents has been performed by utilizing their dynamic <@D11@>D1H- and <@D113@>D1C-NMR, <@D1119@>D1Sn-NMR, and X-ray analyses. Thus, it was clarified that chair-type 3-silyloxy-substituted glutaric anhydride and glutarimide and the chair-type cyclohexanones possessing alkoxy or silyloxy group at the C4 position can predominantly adopt each corresponding substituent-axial conformer in their solution. Similar axial or pseudoaxial preference of silyloxy and benzyloxy groups at C4 of chair-type thiane-1-oxides, thiane-1, 1-dioxides, and dihydrothiines was recognized on their dynamic <@D11@>D1H-NMR spectra. Such axial preference of alkoxy and silyloxy groups of several six-membered compounds was also observed in their crystallographic structures. Existence of the electron-withdrawing moiety ((]SY.di-substituted left.[)C=O, (]SY.di-substituted left.[)SO, (]SY.di-substituted left.[)SO<@D22@>D2) and the low basicity of silyloxy- and alkoxy-oxygen atom proved to be essential for adopting the axial conformer, which could be rationalized in terms of a general hypothesis ; stabilization of the axial conformer due to C3, 5-Hsigma, C4-Osigma<@D1*@>D1 orbital overlap.Several molecules, adopting a bent conformation stacked with both aromatics such as triazoles and benzene derivatives, have been developed and characterized by X-ray crystallographic and ^1H-NMR analyses. Bridging both aromatic moieties with a sulfonic ester bond seems to be an essential factor for the bent conformation. Design and synthesis of new molecules adopting a unique sigmoid conformation have been achieved on the basis of a molecular mechanic calculation.

本文利用动态<@D111 @> D1 H-和<@D113@>D1C-NMR、<@D1119@> D1 Sn-NMR和X射线分析，对具有烷氧基和硅氧基取代基的六元环化合物进行了构象分析。因此，这是明确的，椅型3-甲硅烷基氧基取代的戊二酸酐和戊二酰亚胺和椅型环己酮具有烷氧基或甲硅烷基氧基基团在C4位置可以占主导地位，采取各自相应的取代基轴向构象在其溶液中。在动态<@D11@> D1 H-NMR谱上，发现椅型硫杂环丁烷-1-氧化物、硫杂环丁烷-1，1-二氧化物和二氢硫杂环丁烷的C4位上的硅氧基和苄氧基具有类似的轴向或拟轴向优先性。在一些六元化合物的晶体结构中也观察到烷氧基和硅氧基的轴向选择性。存在吸电子部分（（）SY. [)C=O，（]SY. [)SO，（]SY. [)SO<@D22@>D2）和低碱度的硅氧和烷氧基氧原子被证明是采用轴向构象的必要条件，这可以用一般假设来合理化;由于C3，5-Hsigma，C4-Osigma<@D1*@>D1轨道重叠而使轴向构象稳定。几种分子，采用与两种芳族化合物如三唑和苯衍生物堆叠的弯曲构象，已经开发并通过X射线晶体学和^1H-NMR分析表征。用磺酸酯键桥接两个芳族部分似乎是弯曲构象的重要因素。在分子力学计算的基础上，设计和合成了具有独特S形构象的新分子。

项目成果

Y.Nagao: "Preferential Conformation of the Six-Membered Ring Bearing Alkoxy (or Silyloxy) and Tributyl Stannyl Groups at the Geminal Position" J.Org.Chem.

Y.Nagao：“在孪位位置带有烷氧基（或甲硅烷氧基）和三丁基甲锡烷基的六元环的优先构象”J.Org.Chem。

Y. Nagao: "Axial Preference of Bulky Group- and Electron-Withdrawing Group-Substituted Oxygen Atom on the Chair-Type-Cyclohexanone, -Glutaric Anhydride, and -Glutarimede" Chemistry Letters. 1503-1506 (1990)

Y. Nagao：“椅型环己酮、戊二酸酐和戊二酰亚胺上大基团和吸电子基团取代的氧原子的轴向偏好”化学快报。

Y.Nagao: "Biomimetic,Chemical,and Spectroscopic Evaluations for the Radiosensitizing Potential of N1-and N2-Substituted Derivatives of 3-Nitro-1,2,4-triazole toward Hypoxic Cells in the Radiotherapy:Remarkably Different Substitution Effect" Tetrahedron. 4

Y.Nagao：“3-硝基-1,2,4-三唑的 N1 和 N2 取代衍生物对放射治疗中缺氧细胞的放射增敏潜力的仿生、化学和光谱评估：显着不同的替代效应”四面体。

Y. Nagao: "Design and Synthesis of New Molecules Adopting a Unique Sigmoid Conformation Stacked with Aromatic Moieties" Chemistry Letters.

Y. Nagao：“采用独特的 S 形构象与芳香族部分堆叠的新分子的设计和合成”化学快报。

Y. Nagao: "Preferential Conformation of the Six-Membered Ring Bearing Alkoxy (or Silyloxy) and Tributyl Stannyl Groups at the Geminal Position" J. Org. Chem.

Y. Nagao：“在孪位位置带有烷氧基（或甲硅烷氧基）和三丁基甲锡烷基的六元环的优先构象”J. Org。