Regio- and Stereospecificity in Cationic Cyclopolymerization of 1,2:5,6-Dianhydro-D-mannitols and Synthesis of Poly[(1.fwdarw.6)-2,5-anhydro-3,4-di-O-ethyl-D-glucitol]

Kakuchi, Toyoji; Satoh, Toshifumi; Umeda, Satoshi; Hashimoto, Hisaho; Yokota, Kazuaki

doi:10.1021/ma00116a003

Cited by 19 publications

(23 citation statements)

References 7 publications

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“…A absence of 8 units was also confirmed by 13 C-1 H COSY. This indicates that these polymerizations would proceed through the inversion of the configuration at the C-2 or C-5 of 4, i.e., through the SN2 reaction.…”

Section: Discussionmentioning

confidence: 64%

“…The obtained polymers were yellowish-brown semisolids, and soluble in chloroform, methanol, tetrahydrofuran, and water but insoluble in n-hexane, except that the po- Table I. Cationic polymerization of 1,2: 13 C NMR using inverse gated spin decoupling. The area ratios of C-1, C-2, and C-3 in 2,5-anhydro-3,4-di-0-methyl-L-iditol unit to those in -o-mannitol unit were estimated, respectively, and the values were avaraged.…”

Section: Cyclopolymerizationmentioning

confidence: 99%

“…15 In order to confirm the cyclic structural unit in polymer 5, the 13 C NMR spectra of the polymers were compared with those of three 2,5-anhydrohexitols, i.e., 2,5-anhydro-1 ,3,4,6-tetra-0-methyl-o-mannitol (6), -L-iditol (7), and -o-glucitol (8). Table III summarizes the 13 C NMR chemical shifts of these compounds. Although ten peaks were present in the spectrum of 8, only five peaks were found in each of the spectra, 6 and 7, which reflects the c2 symmetry of compounds 6 and 7.…”

Section: Polymer Structurementioning

confidence: 99%

“…This should be caused by the differences in sequences of the two five-membered repeating units, because the crosspeaks corresponding to six-or seven-membered ring units could not be observed in the 13 C-1 H COSY measurement. The ratio of 2,5-anhydro-3,4-di-0-methyi-Liditol units to -D-mannitol units (y/x) in the polymer was estimated by 13 C NMR using the inverse gated spin decoupling technique and was indicated in Table II. For the anionic cyclopolymerization in 1 ,4-dioxane, the ratio yjx was 1.5, which means that the polymerization was favorable for forming 2,5-anhydro-3,4-di-0-methyi-Liditol unit.…”

Section: + Other Productsmentioning

confidence: 99%

“…The structures of the polymers (5) are discussed by comparing their 13 C NMR spectra with those of 2,5-anhydro-1 ,3,4,6-tetra-0-methyl-o-mannitol t Research Fellow of the Japan Society for the Promotion of Science. tt To whom all correspondence should be addressed.…”

mentioning

confidence: 99%

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Regio- and Stereoselective Cyclopolymerization of 1,2:5,6-Dranhydro-3,4-di-O-methyl-D-glucitol Leading to Polymers with 2,5-Anhydro-3,4-di-O-methyl-D-mannitol and/or -L-iditol Units

Satoh

Hatakeyama

Umeda

et al. 1996

Polym J

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Section: Discussionmentioning

confidence: 64%

Section: Cyclopolymerizationmentioning

confidence: 99%

Section: Polymer Structurementioning

confidence: 99%

Section: + Other Productsmentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Regio- and Stereoselective Cyclopolymerization of 1,2:5,6-Dranhydro-3,4-di-O-methyl-D-glucitol Leading to Polymers with 2,5-Anhydro-3,4-di-O-methyl-D-mannitol and/or -L-iditol Units

Satoh

Hatakeyama

Umeda

et al. 1996

Polym J

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Polymerization of 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐D‐mannitol, 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐L‐iditol, and 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐allitol using zinc complexes: The regio‐ and stereoselectivities and asymmetric synthesis of thiosugar polymers

Satoh

Imai

Sugie

et al. 2005

J. Polym. Sci. A Polym. Chem.

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The polymerizations of the diepisulfides 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐D‐mannitol (1a), 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐L‐iditol (1b), and 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐allitol (1c) were carried out with ZnEt2/H2O, ZnEt2/alcohol, and ZnEt2/(S or R)‐1,1′‐bi‐2‐naphthol (BN) as the initiator systems. All the polymerizations proceeded without any gel formation and gave white, powdery products. The number‐average molecular weights of the obtained polymers were changed in the range of 5300–33,600. The polymerization of 1a using the ZnEt2/H2O (1/1) catalyst in tetrahydrofuran proceeded through a regio‐ and stereoselective cyclopolymerization mechanism to produce thiosugar polymers mainly consisting of 2,5‐anhydro‐1,5‐dithio‐D‐glucitol as the five‐membered ring units. The polymers obtained from 1b and 1c with ZnEt2/H2O exhibited lower stereoregularities than that from 1a. For the polymers obtained from 1a with the ZnEt2/alcohol systems, the molar fraction of the five‐membered ring units depended on the alcohol used as a ligand. On the other hand, the polymerization of 1c using ZnEt2/(R or S)‐BN asymmetrically proceeded, and optically active polymers consisting of desulfurized acyclic units were obtained. When ZnEt2/(R)‐BN (1/1) was used in toluene, the polymer with [α]D23 = +56.9° was obtained in an 88.6% yield. The resulting polymer had an isotactic‐rich structure consisting of about 90% (R)‐configurational units and about 10% (S)‐units. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4118–4125, 2005

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Regio- and stereoselective cyclizations of dianhydro sugar alcohols catalyzed by a chiral (salen)CoIII complex

Satoh

Imai

Umeda

et al. 2005

Carbohydrate Research

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Regio- and Stereospecificity in Cationic Cyclopolymerization of 1,2:5,6-Dianhydro-D-mannitols and Synthesis of Poly[(1.fwdarw.6)-2,5-anhydro-3,4-di-O-ethyl-D-glucitol]

Cited by 19 publications

References 7 publications

Regio- and Stereoselective Cyclopolymerization of 1,2:5,6-Dranhydro-3,4-di-O-methyl-D-glucitol Leading to Polymers with 2,5-Anhydro-3,4-di-O-methyl-D-mannitol and/or -L-iditol Units

Regio- and Stereoselective Cyclopolymerization of 1,2:5,6-Dranhydro-3,4-di-O-methyl-D-glucitol Leading to Polymers with 2,5-Anhydro-3,4-di-O-methyl-D-mannitol and/or -L-iditol Units

Polymerization of 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐D‐mannitol, 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐L‐iditol, and 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐allitol using zinc complexes: The regio‐ and stereoselectivities and asymmetric synthesis of thiosugar polymers

Regio- and stereoselective cyclizations of dianhydro sugar alcohols catalyzed by a chiral (salen)CoIII complex

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