Synthesis of Intelligent Molecule and Structural Study for its Molecular Complexes

智能分子的合成及其分子配合物的结构研究

• 批准号: 04453026
• 负责人: FUKAZAWA Yoshimasa
• 金额: $ 5.06万
• 依托单位: HIROSHIMA 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 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453026/
• 关键词: Recognition; Cyclophane-host; Crownether; Conformational-control; Calix[5]arene; Cation-pi; Metal-transport; Hydrogen-bonding; カリックス[4]アレン; イオン輸送; 疎水性空孔; 選択的包接; シクロファンホスト; ビスクラウンエーテル; 中・大員環状構造; 誘導適合

Chemistry of molecular recognition is the chemistry of intermolecular bond. Since recognition at the molecular level is a fundamental characteristic of biological systems, extensive investigations have been focused on this field. Intermolecular bonds are consist of various interaction, hydrophobic, charge transfer, electrostatic, pi-pi stacking, hydrogen bonding, ion-dipolar interaction and so on. In order to know the main contributing interaction in a molecular complex, it should be clarified the precise structure of the complex in solution. We developed an efficient method for structural analysis of an extremely flexible macrocyclic compound, which utilizes both the molecular mechanics calculation and effect of magnetic anisotropy of aromatic ring current. We have shown that the method can be applicable for the structural elucidation of intermolecular complex in solution. Conformational control for flexible macrocycle is one of the most challenging problems. We attained the control of [m.m]orthocyclophanes having two crown units by complexation of cationic species. Synthetic approach of an allosteric host using this[m.m]orthocyclophanes having two crown units as basic skeleton was carried out. The synthesis of aza-crown ether linked with monodeoxycalix[4]arene was carried out. The compound has potent ability for selective transport of Na cation through organic liquid phase. Calix[5]arene has wider hydrophobic cavity than the smaller congener. We applied this wide cavity for construction of a host molecule by the linkage of dipolar functional groups at its upper rim. Synthesis of the guest molecule having two benzoic acid moieties has carried out. It bound two imidazole molecules in solution. Molecular mechanics calculation using AMBER force field implemented in MacroModel has disclosed that one imidazolium ion is encapsulated in the hydrophobic cavity with an aid of cation-pi interaction to calizarene pi-wall. The second imidazolium ion was bound by the two carbo

分子识别化学就是分子间键的化学。由于在分子水平上的识别是生物系统的基本特征，广泛的研究已经集中在这个领域。分子间键由各种相互作用组成，疏水、电荷转移、静电、π - π堆叠、氢键、离子-偶极相互作用等。为了了解分子配合物中起主要作用的相互作用，必须弄清楚溶液中配合物的精确结构。本文提出了一种利用分子力学计算和芳香环电流磁各向异性效应对极柔性大环化合物进行结构分析的有效方法。结果表明，该方法可用于溶液中分子间络合物的结构解析。柔性大环的构象控制是最具挑战性的问题之一。我们达到了对[m]的控制。由阳离子络合而成的具有两个冠单位的正环烷。利用该方法合成变构宿主的方法[m]。M]具有两个冠单元作为基本骨架的正环烷。研究了单脱氧杯芳烃键合氮杂冠醚的合成。该化合物在有机液相中具有较强的钠离子选择性输运能力。杯状芳烃的疏水腔比其较小的同系物更宽。我们应用这个宽腔构建宿主分子的链接偶极官能团在其上缘。合成了具有两个苯甲酸基团的客体分子。它结合了溶液中的两个咪唑分子。利用MacroModel中实现的AMBER力场进行分子力学计算，发现一个咪唑离子通过阳离子- π相互作用被包裹在疏水腔中。第二个咪唑离子被两个碳原子束缚

项目成果

Y.Fukazawa: "Synthesis and Structure of [3.3]Orthocyclophane" Bulletan Chemical Society of Japan. 66. 1239-1243 (1993)

Y.Fukazawa：“[3.3]Orthocyclophane 的合成和结构”日本化学会公报。

Y.Fukazawa: "Synthesis of Monodeoxycalix[4]arene and Its Dimer Structure in Solution" Tetrahedron Letters. 33. 5803-5806 (1992)

Y.Fukazawa：“单脱氧杯[4]芳烃的合成及其在溶液中的二聚体结构”四面体快报。

Y.Fukazawa: "Syntheis and Structure of [3.3]Orthocyclophane" Bull.Chem.Soc.Jpn.66. 1239-1243 (1993)

Y.Fukazawa：“[3.3]Orthocyclophane 的合成和结构”Bull.Chem.Soc.Jpn.66。

Y.Fukazawa: "Synthesis, Structure, and Physical Properties of 1,11-o-Benzeno[2]ortho-cyclo[2](1,2)tropyliophane" Tetrahedron Letters. 34. 8493-8496 (1993)

Y.Fukazawa：“1,11-o-苯并[2]邻环[2](1,2)tropyliophane的合成、结构和物理性质”四面体快报。

Y.Fukazawa: "Steric Strain in Syn[2.2]metacyclophane" Tetrahedron Letters. 34. 3787-3788 (1993)

Y.Fukazawa：“Syn[2.2]metacyclophane 中的空间应变”四面体字母。