Zhao Dan, Li Zheng-Qiu, Cao Fei, Liang Miao-Miao, Pittman Charles U, Zhu Hua-Jie, Li Li, Yu Shi-Shan
Chinese Center for Chirality, College of Pharmacy, Hebei University, Baoding, Heibei, China.
Department Chemistry, Mississippi State University, State College, Mississippi, USA.
Chirality. 2016 Aug;28(8):612-7. doi: 10.1002/chir.22621. Epub 2016 Jul 18.
This study discusses the choice of different simplified models used in computations of electronic circular dichroism (ECD) spectra and other chiroptical characteristics used to determine the absolute configuration (AC) of the complex natural product sibiricumin A. Sections of molecules containing one chiral center with one near an aromatic group have large effects on the ECD spectra. Conversely, when the phenyl group is present on a substituent without a nonstereogenic center, removal of this section will have little effect on ECD spectra. However, these nonstereogenic-center-containing sections have large effects on calculated optical rotations (OR) values since the OR value is more sensitive to the geometries of sections in a molecule. In this study, the wrong AC of sibiricumin A was reassigned as (7R,8S,1'R,7'R,8'S)-. Chirality 28:612-617, 2016. © 2016 Wiley Periodicals, Inc.
本研究讨论了在计算电子圆二色性（ECD）光谱以及用于确定复杂天然产物西伯利亚霉素A的绝对构型（AC）的其他手性光学特性时所使用的不同简化模型的选择。含有一个手性中心且其中一个靠近芳族基团的分子部分对ECD光谱有很大影响。相反，当苯基存在于没有非立体异构中心的取代基上时，去除该部分对ECD光谱几乎没有影响。然而，这些含有非立体异构中心的部分对计算出的旋光（OR）值有很大影响，因为OR值对分子中各部分的几何形状更敏感。在本研究中，西伯利亚霉素A的错误AC被重新指定为(7R,8S,1'R,7'R,8'S)-。《手性》28:612 - 617，2016年。© 2016威利期刊公司。
