Stereoselective gold(I)-catalyzed approach to the synthesis of complex alpha-glycosyl phosphosaccharides
Zhang, Xiaojuan; Yang, Yutong; Ding, Jiahao; Zhao, Yun; Zhang, Hongbin; Zhu, Yugen*
NATURE COMMUNICATIONS
Volume13 Issue1 Article Number421
DOI:10.1038/s41467-022-28025-0
Published: JAN 20 2022
https://www.nature.com/articles/s41467-022-28025-0
Abstract
Glycosyl phosphosaccharides represent a large and important family of complex glycans. Due to the distinct nature of these complex molecules, efficient approaches to access glycosyl phosphosaccharides are still in great demand. Here, we disclose a highly efficient and stereoselective approach to the synthesis of biologically important and complex alpha-glycosyl phosphosaccharides, employing direct gold(I)-catalyzed glycosylation of the weakly nucleophilic phosphoric acid acceptors. In this work, the broad substrate scope is demonstrated with more than 45 examples, including glucose, xylose, glucuronate, galactose, mannose, rhamnose, fucose, 2-N-3-2-deoxymannose, 2-N-3-2-deoxyglucose, 2-N-3-2-deoxygalactose and unnatural carbohydrates. Here, we show the glycosyl phosphotriester prepared herein was successfully applied to the one-pot synthesis of a phosphosaccharide from Leishmania donovani, and an effective preparation of a trisaccharide diphosphate of phosphosaccharide fragments from Hansenula capsulate via iterative elongation strategy is realized.
Glycosyl phosphosaccharides represent a large and important family of complex glycans, but are difficult to synthesize efficiently. Here, the authors disclose a stereoselective methodology to make alpha-glycosyl phosphosaccharides, via gold(I)-catalyzed glycosylation of phosphoric acid acceptors.
