Palladium-Catalyzed Direct Stereoselective Synthesis of Deoxyglycosides from Glycals

Abstract

Palladium(II) in combination with a monodentate phosphine ligand enables the unprecedented direct and α-stereoselective catalytic synthesis of deoxyglycosides from glycals. Initial mechanistic studies suggest that in the presence of N-phenyl-2-(di-tert-butylphosphino)pyrrole as the ligand, the reaction proceeds via an alkoxy palladium intermediate that increases the proton acidity and oxygen nucleophilicity of the alcohol. The method is demonstrated with a wide range of glycal donors and acceptors, including substrates bearing alkene functionalities.

Keywords: acetals; asymmetric catalysis; deoxyglycosides; glycosylation; palladium.