Abstract
Ring-opening homo- and copolymerization of a 3-deoxygenated anhydro sugar derivative (1,6-anhydro-2,4-di-O-benzyl-3-deoxy-β-D-ribo-hexopyranose, 1) was carried out using phosphorus pentafluoride as the initiator in dichloromethane. Homopolymerization of 1 at −60°C gave highly stereoregular polymers with α-configuration and with number average molecular weight of 12.8×104–2.9×104. The highest yield was 95.6%. The monomer reactivity ratios in copolymerization of 1 with 1,6-anhydro-2,3,4-tri-O-benzyl-β-D-glucopyranose (2) at −60°C were r1=1.60 and r2=0.73. The equilibrium monomer concentrations ([M]e) of 1 and 2 were 0.029–0.042 mol l−1 and 0.0064 mol l−1, respectively (−60°C). Hydrolysis of 1 and 2 in a solution of trifluoroacetic acid and deuterium oxide (volume ratio of 6:4) proceeded at a respective rate of 2.4×10−5 s−1 and 7.3×10−6 s−1 (60°C). Debenzylation of the homo- and copolymers using sodium in liquid ammonia yielded linear (1→6)-α-D-glucopyranans with different degree of 3-deoxygenation.
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Kobayashi, K., Sumitomo, H. & Shiozawa, H. Regioselectively Modified Stereoregular Polysaccharides XIII. Polymerization of 3-Deoxygenated 1,6-Anhydroglucopyranose Derivative. Polym J 21, 137–146 (1989). https://doi.org/10.1295/polymj.21.137
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DOI: https://doi.org/10.1295/polymj.21.137