Stereospecific Palladium-Catalyzed Direct Glycosylation of Oximes: Access to N-O-Linked Glycosides.

Abstract

A highly efficient, palladium-catalyzed glycosylation between 3,4-O-carbonate glycals and acid-labile oximes is disclosed. This approach features broad substrate scope, high functional group tolerance, and easy scalability, delivering glycosyl oximes in excellent yields with exclusive β-selectivity and retention of Z/E geometries. The power of this method is demonstrated by a set of site-selective transformations of glycosylation products and late-stage glycodiversification of bioactive molecules. Overall, our strategy provides an efficient toolkit for facile access to valuable N-O-linked glycosides.