Abstract

Currently, glycosylation reactions predominantly target classical anomeric positions, with limited exploration of glycosylation at non-classical positions. However, there is ample reason to believe that this area is evolving into the next focal point and hotspot in glycosylation research. Therefore, summarizing and prospecting glycosylation reactions at non-classical positions over the past 5 years is deemed essential. This Minireview provides an overview of these transformations, emphasizing the reaction models and synthetic applications. We hope to stimulate future research to address the unmet synthetic challenges for the discovery of new non-classical glycosides, as well as to enhance the efficiency and overcome limitations of existing methods, especially in the construction of predictable and controllable stereoselective glycosides. By offering a comprehensive overview of the progress, our goal is to inspire further research and innovation in this exciting field.

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