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Simplification of the induced circular dichroism method and its application to biologically active natural products

诱导圆二色性方法的简化及其在生物活性天然产物中的应用

基本信息

批准号：
18590025
负责人：
HOSOI Shinzo
金额：
$ 2.55万
依托单位：
Kyushu University of Health and Welfare
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

项目摘要

1) Circular dichroism in a chiral amide possessing an achiral bhaohthyl chromophoreThe bisignate CD curves were observed at around 240 nm in all binaphthyl amides examined. In a conformational analysis of the derivatives, a close correlation was observed between the signs of exciton chirality and the screw senses of the two 2-naphthoyl groups (positive/clockwise; negative/counterclockwise). A semi-empirical molecular orbital calculation (AM1) suggested an intramolecular hydrogen bonding. The CD spectra of the antipodal amides changed into split curves centered at 225 nm after N-methylation. Furthermore, the calculated screw senses between the electric transition moments of the binaphthyl system in N-methyl amides were in good accordance with those expected from their exciton chiralities, indicating a possible application for determination of absolute configuration.2) Induced circular dichroism and conformational analysis of 2.2'-binaphthyl esters derived from primary alcohols possessing a stereogenic center in the β-positionInduced bisignate CD curves were observed near 240 nm in all 2, 2'-binaphthyl esters derived from primary alcohols with a chiral center in the p-position of the hydroxyl group. Conformational analyses of the esters by molecular mechanics were performed. In some cases, the calculated screw sense between the two longitudinal transition moments of 2-naphthoate groups for the most stable conformer with clockwise or counterclockwise orientation was found to be different from that expected from their exciton chiralities. Therefore, CD calculations and conformational analyses of the two esters having strong or moderate interaction between the functional group of the substrate and the ester group of the 2-naphthoate were carried out by the time-dependent density functional theory (TD-DFT). The results suggested that the TD-DFT is strongly effective for determination of the absolute configuration of binaphthyl esters.

1)具有非手性联萘酰胺的圆二色性在240 nm附近观察到双符号CD曲线。在衍生物的构象分析中，观察到激子手性的迹象和两个2-萘甲酰基的螺旋感（正/顺时针;负/逆时针）之间的密切相关性。半经验分子轨道计算（AM 1）建议分子内氢键。对映体酰胺类化合物经N-甲基化后，CD谱变为以225 nm为中心的劈裂曲线。此外，计算得到的N-甲基酰胺中联萘体系的电跃迁矩之间的旋向与根据其激子手性所预期的旋向一致，2）β-环上具有立体中心的伯醇衍生的2，2 ′-联萘酯的诱导圆二色性和构象分析在240 nm附近观察到所有由羟基对位上具有手性中心的伯醇衍生的2，2 '-联萘酯的诱导双符号CD曲线。通过分子力学对酯的构象进行了分析。在某些情况下，2-萘甲酸酯基团的两个纵向过渡时刻之间的螺旋方向的顺时针或逆时针方向的最稳定的构象被发现是不同的预期从他们的激子手征性。因此，CD计算和构象分析的两个酯之间的功能基团的底物和2-萘甲酸酯基团之间的强或中等的相互作用进行的时间依赖密度泛函理论（TD-DFT）。结果表明，TD-DFT方法对确定联萘酯的绝对构型是非常有效的。