Pd-initiated C1 polymerization of diazoacetates with hydroxy-protected sugar substituents: syntheses of a new type of protected sugar-containing C1 polymer (C1 glycopolymer)

Abstract

Pd-initiated C1 polymerization of protected sugar-containing diazoacetates is described. A primary hydroxy group of glucose and galactose whose secondary hydroxy groups were all protected by acetyl, benzyl, or isopropylidene groups was successfully diazoacetylated, and the resulting diazoacetate monomers were polymerized with Pd-based initiators to afford a new type of glycopolymer, where the protected sugar units were densely packed around the polymer main chain. The introduction of a spacer between the protected sugar unit and the diazoacetyl group was found to be effective for high M_n polymer syntheses. Copolymerization of a protected sugar-containing diazoacetate with ethyl and benzyl diazoacetates and the thermal properties of the protected sugar-containing C1 (co)polymers are also described.