Interrupted Pummerer Reaction in Latent‐Active Glycosylation: Glycosyl Donors with a Recyclable and Regenerative Leaving Group

作者：Penghua Shu, Xiong Xiao, Yueqi Zhao, Yang Xu, Wang Yao, Jinyi Tao, Hao Wang, Guangmin Yao, Zimin Lü, Jing Zeng, Qian Wan · 发表于：Angewandte Chemie International Edition · 年份：2015 · DOI：10.1002/anie.201507861 · 被引用次数：74 · 研究领域：Carbohydrate Chemistry and Synthesis、Natural product bioactivities and synthesis、Glycosylation and Glycoproteins Research

Latent O-glycosides, 2-(2-propylthiol)benzyl (PTB) glycosides, were converted into the corresponding active glycosyl donors, 2-(2-propylsulfinyl)benzyl (PSB) glycosides, by a simple and efficient oxidation. Treatment of the PSB donor and various acceptors with triflic anhydride provided the desired glycosides in good to excellent yields. The leaving group, which was activated by an interrupted Pummerer reaction, can be recycled (PSB-OH) and regenerated as the precursor (PTB-OH). A natural hepatoprotective glycoside, leonoside F, was efficiently synthesized in a convergent [3+1] manner with this newly developed method. The present total synthesis also led to a structural revision of this phenylethanoid glycoside.