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Cyclic ketene acetals (CKAs) are among the most well-studied monomers for radical ring-opening polymerization (rROP). However, ring-retaining side reactions and low reactivities in homopolymerization and copolymerization remain significant challenges for existing CKAs. Here, we report that a class of monosaccharide CKAs can be facilely prepared from a short and scalable synthetic route and can undergo quantitative, regiospecific, and stereoselective rROP. NMR analyses and degradation experiments revealed a reaction mechanism involving a propagating radical at the C2 position of pyranose, with different monosaccharides exhibiting distinct stereoselectivity in the radical addition of the monomer. Furthermore, adding maleimide was found to improve the incorporation efficiency of the monosaccharide CKA in the copolymerization with vinyl monomers, producing unique degradable terpolymers with carbohydrate motifs in the polymer backbone.