Stereoselective P(III)-Glycosylation for the Preparation of Phosphinated Sugars

Most of the reported work focus on the development of O-, N-, C- and S-glycosylation methods. However, no study explores P(III)-glycosylation reaction. Herein we describe a convenient protocol to realize P(III)-glycosylation process. A simple β-phosphino ester is adopted as P(III)-transfer reagent for this new type of glycosylation via a nucleophilic substitution and release strategy. Diverse phosphine units are introduced to the anomeric center of various sugars efficiently and with excellent stereoselectivity. The value of this method is showcased by the prepared P(III)-sugars as novel linkers in bioactive molecule conjugation, new chiral ligands in metal-catalyzed asymmetric allylic substitutions and organocatalysts. Preliminary mechanistic studies corroborated the designed P(III)-transfer process.