Nickelaelectro-Catalyzed Glycosyl-Donor Activation Enabling α- <i>C</i> -Alkenyl Glycoside Assembly

<i>C</i>-alkenyl glycosides represent an important class of carbohydrates that includes numerous biologically active compounds. We developed a stereoselective and sustainable strategy using anomeric glycosyl halides as radical precursors for reductive alkenylation. This enables efficient anomeric functionalization with excellent α-selectivity through ligand control. Electrochemical halogen-atom transfer (<i>e</i>-XAT) activates the glycosyl donors, avoiding stoichiometric metal reductants and expensive photocatalysts. This method shows broad substrate scope, including diverse oligosaccharides, delivering high yields and stereoselectivity.