Carbohydrates play crucial roles in molecular recognition, signal transduction, and intercellular adhesion. Prevalent on all cell surfaces and extracellular matrices, carbohydrates are important for cellular transformation and enhancements of the structures and functions of the proteomes. 2 Glycosylation, being one of the most important forms of post-translational modifications, modulates various functions in physiological and pathophysiological states and influences pharmacological properties. Particularly, aminosugars are prevalent in a number of bioactive molecules such as chitin, 4 heparin, 5 human milk oligosaccharides, 6 glycoproteins, 7 and broad-spectrum antibiotics, 8 and they are instrumental in a wide range of biological activities. 9 D-GlcNAc itself comprises approximately 32% of all mammalian oligosaccharides, and O-linked b-Nacetylglucosamines (O-GlcNAc) are typical post-translational modifications and can be found in all eukaryotic organisms. 1b Advances in glycosylation methods for constructing glycosides of 2-amino-2-deoxy sugars (e.g. GlcNAc) are essential for improving the understanding of the physiological and pathological processes that are regulated by glycans. 3a