ANALYSIS OF DYNAMIC STRUCTURE WITH CHEMICAL SHIFT SIMULATION METHOD

化学位移模拟法动力结构分析

• 批准号: 15350025
• 负责人: FUKAZAWA Yoshimasa
• 金额: $ 9.6万
• 依托单位: HIROSHIMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15350025/
• 关键词: Chemical Shift Simulation; Induced Magnetic Shielding; New Chiral Auxiliary; Absolute Configuration; Porphvrin Ring Current; 環電流効果; 科学シフト計算法; 二級アルコール体絶対配置; ポルフィリン環電流効果; テトラフェニルポルフィリン; 2級アミン; ビナフチル

Determination of significantly populated conformers in extremely flexible molecules is a matter of long-standing interest. It is desirable to develop an efficient method for the conformational analysis of the flexible compounds. NMR chemical shifts reflect molecular structure. Hence, variation in the local environment affects chemical shieldings, and the change in chemical shifts of nuclei caused by adjacent substituents provides valuable information about the relative arrangement of the nuclei under study with respect to these nearby substituents. The chemical shift changes caused by the nearby substituents can thus be applicable for conformational analysis. From this point of view, we have developed an efficient method for conformational analysis of flexible organic compounds by using chemical shift simulation technique. The followings are the results of the project.(1) Magnetic shielding effects of polar functional groups were successfully estimated and were applied for the conformational analysis of the flexible compounds, including cyclophanes, molecular tweezers, and their supramolecular complexes.(2) A very useful model of porphyrin ring current effect was developed by using a classical line current approximation. It was found that the model can successfully elucidate the structures of several dicarboxylate complexes of Sn^<(IV)> porphyrins in solution.(3) The newly developed method for the conformational analysis by using chemical shift simulation technique was found to be highly efficient for the structure elucidation of flexible organic compounds.

在极其灵活的分子中确定显著填充的构象是一个长期感兴趣的问题。因此，需要开发一种有效的方法来分析柔性化合物的构象。NMR化学位移反映分子结构。因此，局部环境的变化会影响化学屏蔽，相邻取代基引起的原子核化学位移的变化提供了有关所研究的原子核相对于这些附近取代基的相对排列的有价值的信息。因此，附近取代基引起的化学位移变化可用于构象分析。从这个角度出发，我们发展了一种利用化学位移模拟技术对柔性有机化合物进行构象分析的有效方法。以下是该项目的成果。(1)极性官能团的磁屏蔽效应被成功地估计，并应用于灵活的化合物，包括环番，分子钳，及其超分子复合物的构象分析。(2)利用经典的线电流近似，建立了一个非常有用的卟啉环电流效应模型。结果表明，该模型能较好地解释溶液中Sn^（IV）卟啉二羧酸配合物的结构. (3)利用化学位移模拟技术进行构象分析的新方法被发现是非常有效的灵活的有机化合物的结构解析。

项目成果

Yoshimasa Fukazawa: "Calix[4]arene-based ditopic receptor for dicarboxylates"Tetrahedron Letters. 45・11. 2281-2284 (2004)

Yoshimasa Fukazawa：“基于Calix[4]芳烃的二元受体”Tetrahedron Letters 45・11（2004）。

Calix[5]arene-based receptor for dumb-bell shaped C_<120>

基于 Calix[5] 芳烃的哑铃形 C_<120> 受体

• 发表时间: 2005
• 期刊: Bulletin of the Chemical Society of Japan 78・5
• 作者: S.Mori;J.-Y.Shin;S.Shimizu;F.Ishikawa;H.Furuta;A.Osuka;Yoshimasa Fukazawa
• 通讯作者: Yoshimasa Fukazawa

Shielding effect of thioether C-S bond from proton chemical shifts of 4-thia-5α- and 4-thia-5β- androstane-17-ones

硫醚C-S键对4-thia-5α-和4-thia-5β-雄甾烷-17-酮的质子化学位移的屏蔽作用

• 发表时间: 2005
• 期刊: Tetrahedron 61・15
• 作者: S.Mori;J.-Y.Shin;S.Shimizu;F.Ishikawa;H.Furuta;A.Osuka;Yoshimasa Fukazawa;Yoshimasa Fukazawa;Yoshimasa Fukazawa
• 通讯作者: Yoshimasa Fukazawa

Yoshimasa Fukazawa: "Magnetic shielding effect of amine and ammonium groups obtained from proton chemical shifts of androstane derivatives"Tetrahedron Letters. 44・32. 5975-5978 (2003)

深泽吉正：“从雄甾烷衍生物的质子化学位移获得的胺基和铵基的磁屏蔽效应”Tetrahedron Letters 44・32（2003）。

A Model of Porphyrin Ring Current Effect

卟啉环电流效应模型

• 发表时间: 2005
• 期刊: Tetrahedron Lett 46・5
• 作者: Akiko Inagaki;* Shinichi Edure;Shinichi Yatsuda;Munetaka Akita*;Hajime Iwamoto;Hajime Iwamoto;Hajime Iwamoto;Natsuki K.Kubota;Hajime Iwamoto;Hajime Iwamoto;Hajime Iwamoto;Hajime Iwamoto
• 通讯作者: Hajime Iwamoto