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.

溶液中的构象分析是了解有机化合物物理化学性质不可缺少的手段。虽然NMR技术，如距离依赖的nOe和扭转依赖的^3JHH耦合常数被广泛使用，但它并不总是令人满意的。我们最近开发了化学位移模拟，它利用极性官能团的取代基诱导位移（SIS）。这种模拟方法可以计算附近质子在极性取代基上的诱导位移。为了扩大这种独特的方法的构象分析的适用性，我们已经成功地获得了SIS参数的仲胺基团（C-NH-C），这是普遍存在于有机化合物。利用雄甾烷酮骨架的类似程序，应用于获得萘环的磁各向异性。取代诱导位移的成功再现清楚地表明分子动力学和化学位移模拟方法的结合在柔性分子动态结构的构象分析的发展中起着重要作用。结合分子动力学和化学位移模拟，成功地分析了包合物的动态结构。

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）。

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)。

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)。

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）。