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Brønsted acid-catalyzed ring-opening polycondensation of galactose-based cyclic sulfite


We investigated the polymerization behavior of galactose-based cyclic sulfite as a monomer used to develop the graft polymerization preparation of (1 → 2)-galactan from an alcoholic aglycon. Galactose-based cyclic sulfite 6 was prepared from commercially available tri-O-acetyl-D-galactal in 5 steps. Treatment of 6 with catalytic (+)-10-camphorsulfonic acid (CSA) in the presence of water as the initiator exhibited ring-opening polycondensation of 6 to give benzylated (1 → 2)-galactan and complete elimination of SO2 from the main polymer chain. The MALDI-TOF mass spectrum of the obtained polymer showed a simple pattern with even intervals, which suggested formation of benzylated (1 → 2)-galactan with OH groups at both ends. When we used 4-penten-1-ol as the alcohol initiator for polycondensation of 6, we obtained a pentenoyl group-terminated polymer and/or cyclic oligosaccharides. The reaction mechanism for polycondensation of 6 was probed through systematic investigations of polymerization and DOSY spectral measurements of the polymer.

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This work was supported by the Ogasawara Toshiaki Memorial Foundation.

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Correspondence to Yasuhito Koyama.

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Miyazaki, R., Suzuki, M., Shetty, S.S. et al. Brønsted acid-catalyzed ring-opening polycondensation of galactose-based cyclic sulfite. Polym J (2022).

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