Dipartimento di Scienze, Università della Basilicata, Via dell'Ateneo Lucano 10, Potenza 85100, Italy.
Dipartimento di Medicina Molecolare e Traslazionale, Università di Brescia, Viale Europa 11, Brescia 25123, Italy.
Fitoterapia. 2018 Sep;129:78-84. doi: 10.1016/j.fitote.2018.06.013. Epub 2018 Jun 19.
Jonquailine, a new alkaloid recently isolated from Narcissus jonquilla quail, an Amaryllidaceae species cultivated for its flowers fragrance in Europe and USA, shows very significant anti-proliferative activity against several malignant cancer cell types. Although it was reported that this activity is related to the functionalities and to its stereochemistry at C-8 of B ring, the absolute configuration at this stereocenter was not known. Density functional theory (DFT) calculations of chiroptical properties, namely electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and optical rotatory dispersion (ORD) are employed here to complete assignment of absolute configuration of jonquailine, and then, by extension, to its analogues pretazettine and 8-O-methylpretazettine. While ECD is not discriminating and ORD is of limited use, VCD reveals decisive in the task of absolute configuration assignment.
从欧洲和美国种植的用于花卉香味的石蒜科朱顶红属植物中分离得到的新生物碱冬凌草碱，对多种恶性癌细胞类型具有非常显著的抗增殖活性。尽管据报道这种活性与其功能以及 B 环 C-8 位的立体化学有关，但该立体中心的绝对构型尚不清楚。本文采用密度泛函理论（DFT）计算手性光学性质，即电子圆二色性（ECD）、振动圆二色性（VCD）和旋光色散（ORD），以完成对冬凌草碱绝对构型的完整分配，然后扩展到其类似物 pretazettine 和 8-O-甲基 pretazettine。虽然 ECD 没有区别，ORD 的用途有限，但 VCD 在绝对构型分配任务中具有决定性作用。
