Theoretical calculation of electronic circular dichroism of a hexahydroxydiphenoyl-containing flavanone glycoside.
Theoretical calculation of electronic circular dichroism of a hexahydroxydiphenoyl-containing flavanone glycoside.
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DOI：
10.1021/np800146v
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发表时间：
2009-03-27
影响因子：
5.1
通讯作者：
Ferreira, Daneel
中科院分区：
文献类型：
--
作者：
Ding, Yuanqing;Li, Xing-Cong;Ferreira, Daneel
采用含时密度泛函理论（TDDFT）对含六羟基联苯酰基（HHDP）的黄烷酮糖苷mattucinol-7-O-[4″，6 ″-O-（aS）-hexahydroxydiphenoyl]-β-d-glucopyranoside（2）的电子圆二色性（ECD）进行了理论计算.它确定了（2S）-黄烷酮和（aS）-HHDP部分在产生ECD光谱的2的作用，并提供了理论证据的经验ECD规则适用于单体黄烷酮和含HHDP的化合物。在2中实验观察到的在240 nm附近的高振幅正科顿效应（CE）源自（aS）-HHDP发色团，而在260-300 nm区域的低振幅负CE由（aS）-HHDP和（2S）-黄烷酮部分贡献。“接头”葡糖基部分对总体ECD几乎没有影响。看来，2中的各个发色团对整体ECD的贡献是相加的，并且经验规则适用于构型分配。然而，如果如mattucinol-7-O-[4″，6 ″-O-（aR）-hexahydroxydiphenoyl]-β-d-glucopyranoside（3）所示存在（aR）-HHDP发色团，则当将经验规则应用于实验ECD解释时，（aR）-HHDP的主导作用以及（aR）-HHDP和（2S）-黄烷酮部分之间对其总体ECD的相互作用可能会混淆。因此，量化不同发色团的贡献和相互作用的ECD的理论计算对于此类分子的绝对构型的分配是必不可少的。
Time-dependent density functional theory (TDDFT) was employed for theoretical calculation of electronic circular dichroism (ECD) of a hexahydroxydiphenoyl (HHDP)-containing flavanone glycoside, mattucinol-7-O-[4″,6″-O-(aS)-hexahydroxydiphenoyl]-β-d-glucopyranoside (2). It identified the roles of the (2S)-flavanone and (aS)-HHDP moieties in generating the ECD spectrum of 2, and provided theoretical evidence for the empirical ECD rules applicable to monomeric flavanones and HHDP-containing compounds. The experimentally observed high-amplitude positive Cotton effect (CE) around 240 nm in 2 is derived from the (aS)-HHDP chromophore, while the low-amplitude negative CE in the 260–300 nm region is contributed by both the (aS)-HHDP and (2S)-flavanone moieties. The “linker” glucosyl moiety has little effect on the overall ECD. It appears that the respective chromophores in 2 contribute additively to the overall ECD and the empirical rules are applicable for configurational assignment. However, if an (aR)-HHDP chromophore is present as shown in mattucinol-7-O-[4″,6″-O-(aR)-hexahydroxydiphenoyl]-β-d-glucopyranoside (3), the dominant role of the (aR)-HHDP and interaction between the (aR)-HHDP and (2S)-flavanone moieties to its overall ECD may be confusing when applying the empirical rules to experimental ECD interpretation. Thus, theoretical calculation of the ECD that quantifies the contributions and interactions of different chromophores is essential for the assignment of the absolute configuration of such molecules.
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影响因子：
2.9
作者：
Diedrich, C;Grimme, S
通讯作者：
Grimme, S
影响因子：
3.8
作者：
Slade, D;Ferreira, D;Marais, JPJ
通讯作者：
Marais, JPJ
DOI：
10.1039/p29930000799
发表时间：
1993-05-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
影响因子：
--
作者：
KLAMT, A;SCHUURMANN, G
通讯作者：
SCHUURMANN, G
影响因子：
2.1
作者：
GAFFIELD, W
通讯作者：
GAFFIELD, W
影响因子：
3.6
作者：
Stephens, P. J.;Devlin, F. J.;Cosimelli, B.
通讯作者：
Cosimelli, B.