Abstract
Four 1,6-anhydro-β-D-galactopyranoses having benzoyl derivatives in position 2 and benzyl derivatives in positions 3 and 4 were synthesized and polymerized. (1→6)-β-D-Galactopyranan oligosaccharide derivatives (D̅P̅n<7.6) were obtained with PF5 as initiator in dichloromethane at 0 to −40°C from 1,6-anhydro-2-O-benzoyl-3,4-di-O-benzyl-β-D-galactopyranose (1a), 1,6-anhydro-2-O-benzoyl-3,4-di-O-p-bromobenzyl-β-D-galactopyranose (1c), and 1,6-anhydro-2-O-p-bromobenzoyl-3,4-di-O-p-bromobenzyl-β-D-galactopyranose (1d). 1,6-Anhydro-2-O-p-nitrobenzoyl-3,4-di-O-benzyl-β-D-galactopyranose (1b) gave a stereoirregular product of lower molecular weight in lower yield. The apparent rate of polymerization increased in the order of 1b<1a<1c<1d. The formation of β-(1→6)-linked configuration is explained by the mechanism in which the benzoyl group in position 2 took part in the steric retention of the anomeric center during the ring-opening polymerization. Substituent effects on the reactivities of the monomers and growing species are discussed on the basis of the mechanism.
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Kobayashi, K., Ishii, T., Okada, M. et al. Steric Control in Ring-Opening Polymerization of 1,6-Anhydro Galactose Derivatives by Neighboring Group Participation. Polym J 25, 49–57 (1993). https://doi.org/10.1295/polymj.25.49
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DOI: https://doi.org/10.1295/polymj.25.49