Anhydro sugar derivatives polymerization, ring-opening

M. Okada, Y. Yamakawa, and H. Sumitomo, Chemical synthesis of (1 3)-/i-D-glucopyranan by ring-opening polymerization of a 1,3-anhydro sugar derivative, Macromolecules, 24 (1991) 6797-6799. 

M. Ogawa, K. Hatanaka, and T. Uryu, Synthesis of a novel cellulose-type hexopyranan 6-deoxy-(l - 4)-u-L-talopyranan by selective ring-opening polymerization of 1,4-anhydro sugar derivatives, Macromolecules, 24 (1991) 987-992. 

Y. S. Choi, T. Uryu, and T. Yoshida, Synthesis of block copolysaccharides by ring-opening polymerization of anhydro sugar derivatives, Macromol. Chem. Phys., 198 (1997) 2875-2888. 

A number of anhydro sugar derivatives have also been polymerized in ring opening reactions catalyzed by Lewis acids (iO, 34,35,67,122-130, 133,134). These reactions in contrast proceed by an activated chain polymerization like that of a vinyl monomer or more closely like that of tetrahydrofuran which proceeds by means of a propagating trialkyl-oxonium ion on the end of the growing chain (/35) (Fig. 6). 

Figure 1. Synthetic strategy of regiospecifically modified polysaccharides via ring-opening polymerization of anhydro sugar derivatives.

Ring-Opening Polymerization of Anhydro Sugar Derivatives... 

Figure 5. Trialkyloxonium ion mechanism in the ring-opening polymerization of 1,6-anhydro sugar derivatives leading to stereoregular (l- )-a-D-glucopyranans.

T. Uryu, K. Kitano, and K. Matsuzaki, Ring-opening polymerization of 5,6-anhydro-glucose and 5,6-anhydro-allose derivatives. Effect of substitution or configurational difference at the position of sugar monomers on polymerization behavior, J. Polym. Sci., Part A Polym. Chem., 20 (1982) 2181-2194. 

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