Pd-initiated C1 Polymerization of Diazoacetates with Hydroxy-protected Sugar Substituents: Syntheses of a New Type of Protected Sugar-containing C1 Polymers (C1 Glycopolymers)

Abstract

Pd-initiated C1 polymerization of protected sugar-containing diazoacetates is described. A primary hydroxy group of glucose and galactose whose all the secondary hydroxy groups were protected with 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 glycopolymers, 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 thermal properties of the protected sugar-containing C1 (co)polymers are also described.