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.
This is a preview of subscription content, access via your institution
Subscribe to Journal
Get full journal access for 1 year
only $9.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
Prigozy TI, Naidenko O, Qasba P, Elewaut D, Brossay L, Khurana A, et al. Glycolipid antigen processing for presentation by CD1d molecules. Science. 2001;291:664–7.
Maurya R, Sathiamoorthy B, Deepak M. Flavonoids and phenol glycosides from Boerhavia diffusa. Nat Prod Res. 2007;21:126–34.
Carmely S, Roll M, Loya Y, Kashman Y. The structure of eryloside A, a new antitumor and antifungal 4-methylated steroidal glycoside from the sponge Erylus lendenfeldi. J Nat Prod 1989;52:167–70.
Rowan SJ, Cantrill SJ, Cousins GRL, Sanders JKM, Stoddart JF. Dynamic covalent chemistry. Angew Chem Int Ed. 2002;41:898–952.
Lehn JM. Dynamers: Dynamic molecular and supramolecular polymers. Prog Polym Sci. 2005;30:814–31.
Takata T, Koyama Y. Recycling of network polymer exploiting dynamic covalent chemistry: molecular design directed toward novel recyclable materials. Kobunshi. 2008;57:346–9.
Adero PO, Amarasekara H, Wen P, Bohé L, Crich D. The experimental evidence in support of glycosylation mechanisms at the SN1-SN2 interface. Chem Rev. 2018;118:8242–84.
Kulkarni SS, Wang CC, Sabbavarapu NM, Podilapu AR, Liao PH, Hung SC. “One-pot” protection, glycosylation, and protection-glycosylation strategies of carbohydrates. Chem Rev. 2018;118:8025–104.
Das R, Mukhopadhyay B. Chemical O-glycosylations: An overview. ChemistryOpen. 2016;5:401–33.
Sangwan R, Mandal PK. Recent advances in photoinduced glycosylation: oligosaccharides, glycoconjugates and their synthetic applications. RSC Adv. 2017;7:26256–321.
Van der Vorm S, Hansen T, van Hengst JMA, Overkleeft HS, van der Marel GA, Codée JDC. Acceptor reactivity in glycosylation reactions. Chem Soc Rev. 2019;48:4688–706.
Kanie O, Ito Y, Ogawa T. Orthogonal glycosylation strategy in oligosaccharide synthesis. J Am Chem Soc. 1994;116:12073–4.
Mootoo DR, Konradsson P, Udodong U, Fraser-Reid BO. Armed and disarmed n-pentenyl glycosides in saccharide couplings leading to oligosaccharides. J Am Chem Soc. 1988;110:5583–4.
Halcomb RL, Danishefsky SJ. On the direct epoxidation of glycals: application of a reiterative strategy for the synthesis of β-linked oligosaccharides. J Am Chem Soc. 1989;111:6661–6.
Sharkey PF, Eby R, Schuerch C. Chemical synthesis of a (1→2)-D-glucopyranan. Carbohydr Res. 1981;96:223–9.
Yamaguchi H, Schuerch C. Chemical synthesis of (1→2)-α-D-mannopyranan. Biopolymers. 1980;19:297–309.
Ihsan AB, Koyama Y. Substituent optimization of (1→2)-glucopyranan for tough, strong, and highly stretchable film with dynamic interchain interactions. ACS Macro Lett. 2020;9:720–4.
Shetty SS, Koyama Y. One-pot synthesis of glycyrrhetic acid polyglycosides based on grafting-from method using cyclic sulfite. Tetrahedron Lett. 2016;57:3657–61.
Fujitsuka M, Araki K, Kodama T, Hien TTD, Sakuragi M, Shetty SS, et al. Supramolecular control of spin equilibrium and oxidation state in nanohybrids of amphiphilic glycyrrhetic acid derivatives with [Fe(TACN)2]2+. Chem Lett. 2021;50:1142–5.
Nargis M, Ihsan AB, Koyama Y. Bolaamphiphilic properties and pH-dependent micellization of quercetin polyglycoside. RSC Adv. 2019;9:33674–7.
Nargis M, Ihsan AB, Koyama Y. Effects of sugar chain length of quercetin-3-O-glycosides on micellization in aqueous media. Chem Lett. 2020;49:896–9.
Nargis M, Ihsan AB, Koyama Y. Thermoresponsive structure and dye encapsulation of micelles comprising bolaamphiphilic quercetin polyglycoside. Langmuir. 2020;36:10764–71.
Wang B, Xiong DC, Ye XS. Direct C-H trifluoromethylation of glycals by photoredox catalysis. Org Lett. 2015;17:5698–701.
Re RN, Proessdorf JC, La Clair JJ, Subileau M, Burkart MD. Tailoring chemoenzymatic oxidation via in situ peracids. Org Biomol Chem. 2019;17:9418–24.
Benksim A, Beaupère D, Wadouachi A. A novel stereospecific synthesis of glycosyl cyanides from 1,2-O-sulfinyl derivatives. Org Lett. 2004;22:3913–5.
Bemiller JN, Wing RE. Methyl terminal-4-O-methylmalto-oligosaccharides. Carbohydr Res. 1968;6:197–206.
Azuma N, Sanda F, Takata T, Endo T. First observation of equilibrium polymerization of cyclic sulfite. J Polym Sci, Part A: Polym Chem. 1997;35:3235–40.
Kricheldorf HR, Petermann O. New polymer syntheses. 110. Ring-opening polycondensation of two cyclic monomers-polyesters from ethylene sulfite and cyclic anhydrides. Macromolecules. 2001;34:8841–6.
Hirose D, Gazvoda M, Košmrlj J, Taniguchi T. Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents. Chem Sci. 2016;7:5148–59.
Miyazaki R, Nargis M, Ihsan AB, Nakajima N, Hamada M, Koyama Y. Effects of glycon and temperature on self-assembly behaviors of α-galactosyl ceramide in water. Langmuir. 2021;37:7936–44.
This work was supported by the Ogasawara Toshiaki Memorial Foundation.
Conflict of interest
The authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Miyazaki, R., Suzuki, M., Shetty, S.S. et al. Brønsted acid-catalyzed ring-opening polycondensation of galactose-based cyclic sulfite. Polym J (2022). https://doi.org/10.1038/s41428-022-00724-x