Dual Anomeric Stereocontrol in 1,1′-Glycosylation via a Remote Directing 2-(Diphenylphosphinoyl)acetyl Group

The stereoselective construction of 1,1'-glycosidic linkages represents a significant challenge, as it typically results in a mixture of four possible anomers. Herein, we report a novel and efficient method to achieve this transformation leveraging a remote directing 2-(diphenylphosphinoyl)acetyl (DPPA) group on donors for catalytic glycosylation. This approach provides exceptional dual anomeric stereocontrol for both glycosyl donors and acceptors, which we attribute to the DPPA's role as a powerful hydrogen-bonding (H-bonding) acceptor.