Stereodivergent C-(Hetero)Aryl Glycosylation by Ni-Catalyzed Redox-Neutral Cross-Coupling of Glycosyl Sulfonyl Hydrazides

Unprotected C aryl glycosides are ubiquitous in biologically active compounds and are widely used in chemical biology. The stereochemistry at the anomeric carbon of a Cglycoside often dictates its function. Despite past advances in C-glycosylation, methods that provide selective access to both α and β anomers are scarce due to the challenge of controlling stereoselectivity. Herein, we demonstrate that native sugars, when transformed into glycosyl sulfonyl hydrazide precursors, undergo efficient radical cross-coupling with (hetero)aryl halides under redox-neutral nickel catalysis. The method has broad scope and excellent functional group tolerance, enabling the stereodivergent synthesis of diverse C-(hetero)aryl glycosides in either α or β anomeric forms through ligand control.