Stereoselective synthesis of a branched α-decaglucan

Abstract

The first and convergent synthesis of a branched Arca subcrenata Lischke α-decaglucan containing all of the α-(1 → 3), α-(1 → 4), and α-(1 → 6) glycosyl linkages was efficiently achieved. The tri- and tetrasaccharide fragments and fully protected decasaccharide were assembled in a one-pot manner with excellent α-stereoselectivity, which was secured by the synergistic α-directing effects of the TolSCl/AgOTf catalysis system and the remote participation effect or steric β-shielding of functionalized groups at the donor 6-O-position. Low substrate concentration was revealed to favor the α-stereochemical outcome of glycosylations between bulkier building blocks. The synthetic approach established here would be very useful for the preparation of more complex α-glucans containing different types of glycosidic linkages and branched architectures.