Bismuth-Catalyzed Stereoselective 2-Deoxyglycosylation of Disarmed/Armed Glycal Donors.

Bi(OTf) promoted direct and highly stereoselective glycosylation of "disarmed" and "armed" glycals to synthesize 2-deoxyglycosides has been reported. The tunable and solvent-controlled chemoselective activation of deactivated glycal donors distinguishing the competitive Ferrier and 1,2-addition pathways was discovered to improve substrate scope. The practical versatility of the method has been amply demonstrated with the oligosaccharide syntheses and 2-deoxyglycosylation of high-value natural products and drugs.