Minimally Protected and Stereoselective O -Glycosylation of Carboxylic Acid Allows Rapid Access to α-1- O - and 2- O -Acyl Glycosides

作者：Bangxing Hao, Rongxia Li, Panpan Wang, Yingjie Wang, Xiaolong Li, Peng Xu, Qian Zhang, Xinhao Zhu, Xiaojuan Zhang, Yugen Zhu · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c01845 · 被引用次数：19 · 研究领域：Carbohydrate Chemistry and Synthesis、Glycosylation and Glycoproteins Research、Chemical Synthesis and Analysis

We herein reported a catalytic, minimally protected, and highly α-stereoselective glycosylation protocol using carboxylic acid as an acceptor and glycosyl 8-alkynyl-1-naphthoate as a donor, enabling efficient access to unprotected α-1- O - and 2- O -acyl glycosides. This method demonstrates excellent functional compatibility and scope generality, allowing for the glycosylation of a wide range of complex carboxylic acids. Notably, we successfully synthesized two natural products, α-penta- O -galloyl- d -glucopyranose and nyctanthesin A, using this protocol. Mechanistic studies highlighted the crucial role of the 1- O ester functionality in ensuring chemoselectivity and the important contribution of the 2- O functionality in facilitating the reaction.