Chemoenzymatic Synthesis of Narrow-Polydispersity Glycopolymers: Poly(6-O-vinyladipoyl-d-glucopyranose)

Abstract

The glycomonomer 6-O-vinyladipoyl-d-glucopyranose was prepared via lipase catalyzed transesterification of divinyladipate with α-d-glucopyranose in dry acetonitrile and acetone. The desired 6-O regioisomer was obtained in good yield, and its structure was confirmed by correlation NMR spectroscopy. Controlled radical polymerization of the unprotected monomer was performed in protic media using both xanthate and dithiocarbamate as chain transfer agents to give poly(6-O-vinyladipoyl-d-glucopyranose) with M_n of 17 and 19 kDa (SEC) respectively and a polydispersity as low as 1.10. To the best of our knowledge, this is the first example of a narrow-polydispersity, poly(vinyl ester)-like glycopolymer.