Abstract
The present paper is concerned with the applicability of the neighboring group participation of a 2-O-(p-substituted benzoyl) group to the stereoregulation of the ring-opening polymerization of 1,6-anhydro deoxysugar derivatives. 1,6-Anhydro-2-O-(p-substituted benzoyl)-3,4-dideoxy-β-D-erythro-hexopyranoses (5a–d) were polymerized in dichloromethane at different temperatures ranging from −60 and −20°C with phosphorus pentafluoride as an initiator. 1,6-Anhydro-2-O-benzoyl-3-O-benzyl-4-deoxy-β-D-xylo-hexopyranose (7a) and its 2-O-(p-bromobenzoyl) homolog (7b) were also polymerized under similar conditions. 13C NMR analysis revealed that all the polymers were composed of both the respective (1→6)-α- and (1→6)-β-linked structural units. Their proportions varied depending on the p-substituents as well as the reaction conditions: An electron-withdrawing p-substituent on the 2-O-benzoyl aromatic ring reduced the β-unit content of the polymer, although it increased the polymer yield. The presence of a 3-O-benzyl group was favorable for the formation of (1→6)-β-linked structural units. On the basis of these results, factors disturbing the configurational regularity of the anomeric carbons were discussed.
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Okada, M., Kubota, Y. Chemical Synthesis of Polysaccharides XI. Ring-Opening Polymerization of 1,6-Anhydro-2-O-(p-Substituted Benzoyl) Deoxysugar Derivatives. Polym J 24, 1137–1145 (1992). https://doi.org/10.1295/polymj.24.1137
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DOI: https://doi.org/10.1295/polymj.24.1137