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

Chem Asian J. 2024 Feb 16;19(4):e202301013. doi: 10.1002/asia.202301013. Epub 2024 Feb 9.

Abstract

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 H2 18 O labeling, which validates that water (moisture) is a sole source of oxygen.

Keywords: 2,3-unsaturated diarylmethyl O-glycosides; Glycal; Glycosylation; H2O as the oxygen source; Palladium catalysis.