A new procedure for chemical modification of poly(vinyl alcohol) (PVA) was established by a glycosidation reaction of hydroxyl groups in PVA with triacetylated sugar oxazoline 1. 1H and 13C NMR analyses indicated that triacetylated N‐acetyl‐D‐glucosamine (GlcNAc) was introduced onto a PVA backbone selectively via a β‐O‐glycoside linkage. Deacetylation of triacetylated GlcNAc‐substituted PVA 2 resulted in GlcNAc‐substituted PVA 3 in good yield. These modified PVAs 2 and 3 exhibited solubilities and thermal properties different from the original PVA.
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