Palladium-Catalyzed α-Stereoselective O-Glycosylation of O(3)-Acylated Glycals

[Image: see text] Pd(MeCN)(2)Cl(2) enables the α-stereoselective catalytic synthesis of 2,3-unsaturated O-glycosides from O(3)-acylated glycals without the requirement for additives to preactivate either donor or nucleophile. Mechanistic studies suggest that, unlike traditional (η3-allyl)palladium-mediated processes, the reaction proceeds via an alkoxy-palladium intermediate that increases the proton acidity and oxygen nucleophilicity of the alcohol. The method is exemplified with the synthesis of a range of glycosides and glycoconjugates of synthetic utility.