Electrochemical 2-Deoxyglycosylation of <i>N</i> -Containing Molecules with β-Stereoselectivity

<i>N</i>-Glycosides represent a structurally important class of compounds with various applications in the chemical, biological, and pharmaceutical fields. Conventional <i>N</i>-glycosylation methods typically require acidic conditions and face inherent limitations, including poor stereocontrol and narrow substrate tolerance. We herein report an electrochemical approach for the direct 2-deoxyglycosylation of sulfonamides and <i>N</i>-heterocycles using glycals in an undivided cell. This method eliminates the need for chemical oxidants, providing a more sustainable synthetic approach. The reaction proceeds under mild conditions with good to excellent β-stereoselectivity, demonstrates broad functional group compatibility, and is readily scaled up. Notably, this strategy is successfully applied to the <i>N</i>-glycosylation of nonsteroidal anti-inflammatory drug celecoxib. Collectively, this protocol provides a greener and more practical strategy for <i>N</i>-glycosylation, enabling the efficient modification of nitrogen-containing drug molecules.