Stereodivergent <i>C</i> ‐(Hetero)Aryl Glycosylation by Nickel‐Catalyzed Redox‐Neutral Cross‐Coupling of Glycosyl Sulfonyl Hydrazides

Abstract

ABSTRACT 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 C ‐glycoside 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.