Xylose-derived thionocarbamates as a synthetic handle towards a functional platform of sugar-based polymers

The derivatisation of d-xylose with potassium thiocyanate is presented as a versatile synthetic handle towards functional synthetic carbohydrate polymers. The reactivity of the resulting 1,3-oxazolidine-2-thione (OZT) group with alkyl bromides is ubiquitous and, herein, has been exploited to synthesise seven bio-derived monomers with different pendant functionalities. These monomers were polymerised with dithiols to yield functional poly(ester-thioethers) with a broad spectrum of properties. From a single non-functionalised OZT-polymer, a variety of post-polymerisation modification approaches are possible to functionalise the materials with different pendant groups. These results present a novel simple methodology to tailor the properties of synthetic carbohydrate polymers to different applications. The derivatisation of d-xylose with potassium thiocyanate, then reactivity with alkyl bromides, is presented as a versatile synthetic handle towards functional synthetic carbohydrate polymers, including via post-polymerisation modifications.