Palladium-Catalyzed Stereospecific Glycosylation Enables Divergent Synthesis of N-O-Linked Glycosides.

We present a versatile palladium-catalyzed glycosylation platform that enables facile access to structurally diverse N-O-linked glycosides with constantly excellent regio- and stereoselectivities. Importantly, this approach offers a broad substrate scope, low catalyst loadings, and outstanding chemoselectivity, allowing for the selective reaction of oximes/hydroximic acids over hydroxyl groups that would otherwise pose challenges in conventional glycosylation methods. The synthetic utility of this method is further exemplified through a range of synthetic transformations and late-stage modification of bioactive molecules. Overall, our method provides an efficient toolkit for the synthesis of N-O-linked glycosides, which will facilitate their subsequent biological evaluations.