Regioselective deacetylation of peracetylated glycosides with a cleavable aglycone

Partially acetylated carbohydrates are integral to several biological functions and serve as synthetic intermediates for accessing complex glycoconjugates and oligosaccharides; however, their chemical synthesis remains highly challenging. Herein, we describe a straightforward protocol for the synthesis of monoacetylated sugars through acid-catalyzed regioselective deacetylation of readily accessible peracetylated glycosides featuring a cleavable aglycone (4-methoxyphenyl). The protocol proved effective for β-1,2-trans and α-1,2-cis-configured peracetylated pyranosides and its utility was demonstrated by large-scale synthesis, optimization for continuous flow, and application towards oligosaccharide synthesis.