An Open-Air Palladium-Catalyzed Stereoselective O-Glycosylation of Glycals via in-situ Generation of gem-Disubstituted Methanols from p-Quinone Methides.

We devised a palladium-catalyzed α-stereoselective glycosylation that incorporates oxygen via in-situ generation of gem-disubstituted methanols from p-quinone methides to access 2,3-unsaturated gem-diarylmethyl O-glycosides under open-air atmosphere at room temperature. Advantages of this environmentally friendly strategy include the absence of additives and ligands, using water as the green source of oxygen, mildest, operationally simple, exhibiting a wide functional group tolerance, and compatibility with a variety of glycal progenitors in appreciable yields. A mechanistic study has been verified via H O labeling, which validates that water (moisture) is a sole source of oxygen.