光诱导的芳香七烯抗真菌抗生素坎地丁 D 向全反式异构体的转化。

Light-Induced Transformation of the Aromatic Heptaene Antifungal Antibiotic Candicidin D into Its All-Trans Isomer.

机构信息

Department of Pharmaceutical Technology and Biochemistry, Faculty of Chemistry , Gdańsk University of Technology , Gabriela Narutowicza Street 11/12 , 80-233 Gdańsk , Poland.

出版信息

J Nat Prod. 2018 Jul 27;81(7):1540-1545. doi: 10.1021/acs.jnatprod.7b00821. Epub 2018 Jun 14.

DOI:10.1021/acs.jnatprod.7b00821

PMID:29901397

Abstract

Illumination of the aromatic heptaene macrolide antifungal antibiotic candicicin D with UV light results in an isomerization of the molecule. The product formed after irradiation of the candicidin complex with UV light (λ = 365 nm), namely, iso-candicidin D, was isolated and subjected to 2D NMR studies, consisting of DQF-COSY, ROESY, TOCSY, HSQC, and HMBC experiments. The obtained spectral data unambiguously evidenced that iso-candicidin D was the all-trans isomer of the native antibiotic, and straightening of the heptaenic chromophore was the only light-induced structural change that occurred. Hence, iso-candicidin D was proclaimed to be a prototype of a novel class of polyene macrolide antifungal antibiotics: the all-trans aromatic heptaenes, containing a macrolide ring similar to that of amphotericin B.

摘要

用紫外光照射芳香七烯大环抗真菌抗生素坎地辛 D 会导致分子的异构化。用紫外线（λ=365nm）辐照坎地辛复合物后形成的产物，即异坎地辛 D，被分离出来，并进行了二维 NMR 研究，包括 DQF-COSY、ROESY、TOCSY、HSQC 和 HMBC 实验。获得的光谱数据明确表明，异坎地辛 D 是天然抗生素的全反式异构体，并且只有七烯发色团的直线化是发生的唯一光诱导结构变化。因此，异坎地辛 D 被宣布为一类新型多烯大环抗真菌抗生素的原型：全反式芳香七烯，含有与两性霉素 B 相似的大环内酯环。