Structural Analysis with NMR Chemical Shift calculation

通过 NMR 化学位移计算进行结构分析

• 批准号: 12045248
• 负责人: FUKAZAWA Yoshimasa
• 金额: $ 6.85万
• 依托单位: Graduate school of science, Hiroshima-University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12045248/
• 关键词: Chemical Shift Simulation; Secondary amine; Binaphtyl; Substituent induced shift; Chiral auxiliary; Absolute configuration secondary alcohol; Supramolecule; Dynamica structure; 二級アルコール; 絶対配置; 環電流効果; 磁気異方性発色団; 分子動力学計算; NMR化学シフト; 構造解析; 立体配座 /

Conformational analysis in solution is indispensable for understanding of physical and chemical properties of organic compound. While NMR techniques such as distance-dependent nOe and torsion-dependent ^3JHH coupling constants were used extensively, it is not always satisfactory. We have recently developed chemical shift simulation, which utilizes the substituent induced shifts (SIS) of polar functional groups. This simulation method can calculate the induced shift of a near-by proton from a polar substituent. To widen the applicability of this unique method for conformational analysis, we have succeeded to obtain the SIS parameters of the secondary amine group (C-NH-C) which is ubiquitous in organic compounds. Similar procedure using androstanone skeletons was applied to obtain the magnetic anisotropy of naphthalene ring. The successful reproduction of the substitution induced shifts clearly indicates that the combination of the molecular dynamics and the chemical shift simulation method play an important role in the development of the conformational analysis of the dynamic structure of the flexible molecules. The dynamic structure of inclusion complexes was also successfully analyzed by the combination of the molecular dynamics and the chemical shift simulation.

溶液中的构象分析对于理解有机化合物的物理和化学特性是必不可少的。尽管广泛使用了诸如距离依赖性NOE和扭转依赖性 ^3JHH耦合常数之类的NMR技术，但并不总是令人满意。我们最近开发了化学位移模拟，该化学位移模拟利用了极性官能团的取代诱导的移位（SIS）。这种仿真方法可以计算近似质子从极性取代基的诱导转移。为了扩大这种独特的构象分析方法的适用性，我们成功地获得了在有机化合物中无处不在的二级胺基（C-NH-C）的SIS参数。使用雄激素骨架的类似程序，以获得萘环的磁各向异性。取代诱导的移位的成功再现清楚地表明，分子动力学和化学移位模拟方法的组合在柔性分子动态结构的构象发展中起着重要作用。通过分子动力学和化学移位模拟的组合，还成功地分析了包含复合物的动态结构。

项目成果

Yoshimasa Fukazawa: "Fullerene sensors based on calix[5]arene."Chemical Communication. 2002. 2148-2149 (2002)

Yoshimasa Fukazawa：“基于杯[5]芳烃的富勒烯传感器。”化学通讯。

Yoshimasa Fukazawa: "Fullerene sensors based on calix[5]arene"Chemical Communication. 2002・18. 2148-2149 (2002)

深泽芳正：“基于杯[5]芳烃的富勒烯传感器”化学通讯2002・18（2002）。

Y.Fukazawa: "Flexible Molecular Tweezers Based on a Dioxa[2.2]orthocyclophane Linked with Weak Electron Acceptor"Tetrahedron Letters. 41・21. 4139-4142 (2000)

Y. Fukazawa：“基于与弱电子受体连接的二氧杂环己烷[2.2]的柔性分子镊子”四面体快报41・21（2000）。

Y.Fukazawa: "Layered donor-acceptor-acceptor arrangement in complex of molecular tweezers based on dioxa[2.2]orthocyclophane,"Tetrahedron Letters. 41・4. 477-480 (2000)

Y. Fukazawa：“基于二氧杂[2.2]正环烷的分子镊子复合物中的分层供体-受体-受体排列”，Tetrahedron Letters 41・4 (2000)。

Yoshimasa Fukazawa: "On-beads screenibg of solid-attached diketopiperazines for calix[5]arene-based receptor"Tetrahedron Letters. 44・20. 3889-3892 (2003)

Yoshimasa Fukazawa：“基于杯[5]芳烃的受体的固体附着二酮哌嗪的珠上筛选”Tetrahedron Letters 44・20 3889-3892 (2003)。