Diastereoselective Synthesis of <i>N</i>-Glycosides via Buchwald–Hartwig Coupling

Herein we report a practical and highly efficient methodology for the β-selective synthesis of <i>N</i>-glycosides via Buchwald-Hartwig coupling. This glycosylation strategy employs glycosyl chloride with different amine aglycones and is catalyzed by an inexpensive copper(I) catalyst under mild, ligand-free conditions. The synthetic applicability is further demonstrated through the gram-scale reaction and the late-stage functionalization of bioactive molecules. Mechanistic insights and the critical role of the glycosyl iodide intermediate in the catalytic cycle are highlighted.