The composition, sequence, length and type of glycosidic linkage of polysaccharides profoundly affect their biological and physical properties. However, investigation of the structure-function relationship of polysaccharides is hampered by difficulties in accessing well-defined polysaccharides in sufficient quantities. Here we report a chemical approach to precision polysaccharides with native glycosidic linkages via living cationic ring-opening polymerization of 1,6-anhydrosugars. We synthesized well-defined polysaccharides with tunable molecular weight, low dispersity and excellent regio- and stereo-selectivity using a boron trifluoride etherate catalyst and glycosyl fluoride initiators. Computational studies revealed that the reaction propagated through the monomer α-addition to the oxocarbenium and was controlled by the reversible deactivation of the propagating oxocarbenium to form the glycosyl fluoride dormant species. Our method afforded a facile and scalable pathway to multiple biologically relevant precision polysaccharides, including D-glucan, D-mannan and an unusual L-glucan. We demonstrated that catalytic depolymerization of precision polysaccharides efficiently regenerated monomers, suggesting their potential utility as a class of chemically recyclable materials with tailored thermal and mechanical properties.
© 2023. The Author(s), under exclusive licence to Springer Nature Limited.