Stereocontrolled Access to N-Glycosides via Nickel-Catalyzed Reductive C(sp 3 )−N(sp 3 ) Cross-Coupling

N-Glycosides are pivotal in diverse biological processes and have garnered significant attention in chemistry, biology, and modern therapeutics. However, conventional synthetic methods, predominantly relying on ionic N-glycosylation with amine nucleophiles under acidic conditions, suffer from inherent limitations such as poor stereoselectivity and limited product diversity. Herein, we report a robust and highly stereoselective approach to N-glycosides via nickel-catalyzed reductive coupling of glycosyl bromides with electrophilic amines. This method exhibits broad functional group compatibility and delivers N-glycosides with β-selectivity. The synthetic utility is demonstrated by the rapid assembly of diverse glycosyl primary amine-derived building blocks and the late-stage functionalization of bioactive molecules. Finally, N-glycoside compound 3b exhibits potential anticancer activity, further highlighting the utility of this methodology. A DFT calculation profile revealed the mechanism of this nickel-catalyzed N-glycosylation reaction.