Electrochemical 2-Deoxyglycosylation of N-Containing Molecules with β-Stereoselectivity.

N-Glycosides represent a structurally important class of compounds with various applications in the chemical, biological, and pharmaceutical fields. Conventional N-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 N-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 N-glycosylation of nonsteroidal anti-inflammatory drug celecoxib. Collectively, this protocol provides a greener and more practical strategy for N-glycosylation, enabling the efficient modification of nitrogen-containing drug molecules.