Electrochemical Glycosylation via Halogen-Atom-Transfer for C -Glycoside Assembly.

Glycosyl donor activation emerged as an enabling technology for anomeric functionalization, but aimed primarily at O -glycosylation. In contrast, we herein disclose mechanistically distinct electrochemical glycosyl bromide donor activations via halogen-atom transfer and anomeric C -glycosylation. The anomeric radical addition to alkenes led to C -alkyl glycoside synthesis under precious metal-free reaction conditions from readily available glycosyl bromides. The robustness of our e-XAT strategy was further mirrored by C -aryl and C -acyl glycosides assembly through nickela-electrocatalysis. Our approach provides an orthogonal strategy for glycosyl donor activation with expedient scope, hence representing a general method for direct C -glycosides assembly.