Absolute configuration of diterpenoids from Jatropha dioica by vibrational circular dichroism

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• 作者：Eleuterio Burgueñ ; o-Tapia^a ; ^{eleuteriobt@gmail.com} ; Katia Chá ; vez-Castellanos^a ; Ernestina Cedillo-Portugal^b ; Pedro Joseph-Nathan^c
• 刊名：Tetrahedron: Asymmetry
• 出版年：2017
• 出版时间：15 January 2017
• 年：2017
• 卷：28
• 期：1
• 页码：166-174
• 全文大小：1243 K
• 卷排序：28

文摘

The absolute configuration of jatropholone A 1 and B 2, including the possibility to observe the vibrational circular dichroism (VCD) capacity to differentiate between two epimeric compounds in the presence of an inherently dissymmetric chromophore, which normally dominates VCD and electronic circular dichroism (ECD) spectra, followed after comparison of their experimental and DFT calculated VCD spectra, allowed us to conclude that although non-local (M/P) chirality generated by atropisomerism dominates over local chirality generated by an (R/S) change, the stereogenic center can confidently be assigned by VCD after DFT calculations. In addition, the absolute configurations of jatrophatrione 3 and citlalitrione 4, a compound proposed as a taxonomic marker for the genus Jatropha, were assigned by contrasting their respective calculated and experimental IR and VCD spectra. The evaluation of Flack and Hooft parameters obtained from the single-crystal X-ray diffraction data of jatropholone B acetate 6, and of 4 independently confirmed the absolute configurations of these molecules.