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

A highly efficient, palladium-catalyzed glycosylationbetween 3,4-O-carbonate glycals and acid-labile oximesis disclosed.This approach features broad substrate scope, high functional grouptolerance, and easy scalability, delivering glycosyl oximes in excellentyields with exclusive beta-selectivity and retention of Z/E geometries. The power of this methodis demonstrated by a set of site-selective transformations of glycosylationproducts and late-stage glycodiversification of bioactive molecules.Overall, our strategy provides an efficient toolkit for facile accessto valuable N-O-linked glycosides.

Automated summary

A highly efficient palladium-catalyzed glycosylation reaction between 3,4-O-carbonate glycals and acid-labile oximes is described. This method offers a broad substrate scope, high functional group tolerance, and easy scalability, resulting in glycosyl oximes with excellent yields, exclusive β-selectivity, and retention of Z/E geometries. The versatility of this approach is demonstrated through site-selective transformations and late-stage glycodiversification of bioactive molecules. Overall, this strategy provides an efficient toolkit for accessing valuable N-O-linked glycosides.