2-O-N-Benzylcarbamoyl as a Protecting Group To Promote β-Selective Glycosylation and Its Applications in the Stereoselective Synthesis of Oligosaccharides

This study examines the utility of the N-benzylcarbamoyl (BnCar) protecting group in glycosylation reactions of the parent O-2 protected carbohydrate donor. It was found that the BnCar group imparted exclusively beta-selectivity with primary and secondary alcohols. A mechanistic study revealed the activated intermediate to be the glycosyl triflate in a skew conformation, which results in beta-selective glycosylation via an S(N)2-like pathway. The BnCar group can be readily cleaved using tetrabutylammonium nitrite, without affecting ester and ether protecting groups. Taken together, these results show BnCar to be useful for the synthesis of complex oligosaccharides, an undertaking that requires delicate chemical differentiation of various protecting groups.