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Electrochemical Glycosylation via Halogen-Atom-Transfer for <i>C</i>-Glycoside Assembly

Jun Wu, Purushothaman Rajeshwaran, Felix Kallert, Simon L. Homölle, Lutz Ackermann

2024ACS Catalysis37 citationsDOIOpen Access PDF

Abstract

High Resolution Image Download MS PowerPoint Slide 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.

Topics & Concepts

ChemistryGlycosylGlycosylationAnomerGlycosyl donorCombinatorial chemistryArylGlycosideHalogenStereochemistryAlkylOrganic chemistryBiochemistryRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques