一种单一的手性光谱方法可能无法确定非对映异构体：芙蓉酸和藤黄酸二甲酯的绝对构型。
A single chiroptical spectroscopic method may not be able to establish the absolute configurations of diastereomers: dimethylesters of hibiscus and garcinia acids.
机构信息
Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, USA.
出版信息
J Phys Chem A. 2011 Jun 9;115(22):5665-73. doi: 10.1021/jp202501y. Epub 2011 May 13.
Abstract
Electronic circular dichroism (ECD), optical rotatory dispersion (ORD), and vibrational circular dichroism (VCD) spectra of hibiscus acid dimethyl ester have been measured and analyzed in combination with quantum chemical calculations of corresponding spectra. These results, along with those reported previously for garcinia acid dimethyl ester, reveal that none of these three (ECD, ORD, or VCD) spectroscopic methods, in isolation, can unequivocally establish the absolute configurations of diastereomers. This deficiency is eliminated when a combined spectral analysis of either ECD and VCD or ORD and VCD methods is used. It is also found that the ambiguities in the assignment of absolute configurations of diastereomers may also be overcome when unpolarized vibrational absorption is included in the spectral analysis.
摘要
已测量并分析了芙蓉酸二甲酯的电子圆二色性（ECD）、旋光色散（ORD）和振动圆二色性（VCD）光谱，并结合相应光谱的量子化学计算进行了分析。这些结果与以前报道的藤黄酸二甲酯的结果一起表明，这三种光谱方法（ECD、ORD 或 VCD）中的任何一种都不能单独明确确定非对映异构体的绝对构型。当使用 ECD 和 VCD 或 ORD 和 VCD 方法的组合光谱分析时，这种缺陷就被消除了。还发现，当将非偏振振动吸收纳入光谱分析时，也可以克服非对映异构体绝对构型分配的歧义。
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