Centre Armand-Frappier Santé Biotechnologie, Institut National de La Recherche Scientifique (INRS), 531 Boulevard des Prairies, Laval (Québec), H7V 1B7, Canada.
Department of Microbiology, Infectious Disease and Immunology, Montreal Heart Institute, Université de Montréal, 5000 Rue Bélanger, Montréal (Québec), H1T 1C8, Canada.
Carbohydr Res. 2021 Sep;507:108373. doi: 10.1016/j.carres.2021.108373. Epub 2021 Jun 11.
Burkholderia gladioli is a Gram-negative bacterium that biosynthesizes a cocktail of potent antimicrobial compounds, including the antifungal phenolic glycoside sinapigladioside. Herein, we report the total synthesis of the proposed structures of gladiosides I and II, two structurally related phenolic glycosides previously isolated from B. gladioli OR1 cultures. Importantly, the physical and analytical data of the synthetic compounds were in significant discrepancies with the natural products suggesting a misassignment of the originally proposed structures. Furthermore, we have uncovered an acid-catalyzed fragmentation mechanism converting the α,β-unsaturated methyl carbamate-containing gladioside II into the aldehyde-containing gladioside I. Our results lay the foundation for the expeditious synthesis of derivatives of these Burkholderia-derived phenolic glycosides, which would enable to decipher their biological roles and potential pharmacological properties.
译名：生肌藤伯克霍尔德菌
简介：生肌藤伯克霍尔德菌是一种革兰氏阴性细菌，它可以生物合成多种强效抗菌化合物，包括抗真菌的酚糖苷sinapigladioside。在此，我们报告了gladiosides I 和 II 的全合成，这两种结构相关的酚糖苷之前从B. gladioli OR1 培养物中分离出来。重要的是，合成化合物的物理和分析数据与天然产物有很大的差异，这表明最初提出的结构被错误地指定。此外，我们还发现了一种酸催化的断裂机制，该机制将含有α，β-不饱和甲基氨基甲酸酯的gladioside II 转化为含有醛的gladioside I。我们的结果为这些来源于伯克霍尔德菌的酚糖苷衍生物的快速合成奠定了基础，这将有助于破译它们的生物学作用和潜在的药理学特性。
