Synthesis of Glucuronoxylan Hexasaccharides by Preactivation-Based Glycosylations : Synthesis of Glucuronoxylan Hexasaccharides by Preactivation-Based Glycosylations

The synthesis of two glucuronoxylans is described, which both consist of a pentaxylan backbone and a glucuronic acid linked to the 2 position in the fourth xylose residue from the reducing end. The two target molecules differ in the 4 position of the glucuronic acid where one is unsubstituted while the other contains a methyl ether.

The pentaxylan backbone is assembled in four glycosylation reactions with phenyl thioglycoside donors. The couplings are performed by preactivation of the donor with in situ‐generated p ‐nitrobenzenesulfenyl triflate prior to addition of the acceptor. The glucuronic acids are then attached by Koenigs‐Knorr glycosylations followed by deprotections.

The syntheses employ a total of 8 steps from monosaccharide building blocks and afford the two glucuronoxylans in 12 and 15% overall yield. The hexasaccharide products are valuable substrates for investigating the activity and specificity of glucuronoxylan‐degrading enzymes.