Cyclopolymerization of 1,2:5,6-Diepithio-3,4- di-<i>O</i>-methyl-1,2,5,6-tetradeoxy-<scp>d</scp>-mannitol and -<scp>l</scp>-iditol Leading to a Novel Thiosugar Polymer

Satoh, Toshifumi; Kitazawa, Daisuke; Nonokawa, Ryuji; Kamada, Masatoshi; Yokota, Kazuaki; Hashimoto, Hisaho; Kakuchi, Toyoji

doi:10.1021/ma992137j

Cited by 7 publications

(3 citation statements)

References 28 publications

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“…In addition to diepoxides, polymerization of diepisulfides, such as 1,2:5,6-diepithio-3,4-di-O-methyl-1,2:5,6-tetradeoxy-Dmannitol (41) and -L-iditol (42), was reported (Figure 19). 121,122 Similarly to the polymerization of the corresponding diepoxides, 1,2:5,6-dianhydro-3,4-di-O-alkyl-D-mannitols (35) and L-iditols (36), both cationic and anionic polymerizations of those diepisulfides afford polymers containing five-membered 3,4-dimethoxy-1-thiacyclopentylene units. Polymer yield is higher in the anionic polymerization, performed using t-BuOK as the initiator, than the cationic polymerization, performed using BF 3 •OEt 2 as the initiator.…”

Section: Cyclopolymerization Of Diepoxides Diepisulfides and Triepoxidesmentioning

confidence: 99%

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Cyclopolymerizations: Synthetic Tools for the Precision Synthesis of Macromolecular Architectures

2018

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Monomers possessing two functionalities suitable for polymerization are often designed and utilized in syntheses directed to the formation of cross-linked macromolecules. In this review, we give an account of recent developments related to the use of such monomers in cyclopolymerization processes, in order to form linear, soluble macromolecules. These processes can be activated by means of radical, ionic, or transition-metal mediated chain-growth polymerization mechanisms, to achieve cyclic moieties of variable ring size which are embedded within the polymer backbone, driving and tuning peculiar physical properties of the resulting macromolecules. The two functionalities are covalently linked by a "tether", which can be appropriately designed in order to "imprint" elements of chemical information into the polymer backbone during the synthesis and, in some cases, be removed by postpolymerization reactions. The two functionalities can possess identical or even very different reactivities toward the polymerization mechanism involved; in the latter case, consequences and outcomes related to the sequence-controlled, precision synthesis of macromolecules have been demonstrated. Recent advances in new initiating systems and polymerization catalysts enabled the precision syntheses of polymers with regulated cyclic structures by highly regio- and/or stereoselective cyclopolymerization. Cyclopolymerizations involving double cyclization, ring-opening, or isomerization have been also developed, generating unique repeating structures, which can hardly be obtained by conventional polymerization methods.

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Section: Cyclopolymerization Of Diepoxides Diepisulfides and Triepoxidesmentioning

confidence: 99%

“…Figure 19. Polymerization of 1,2:5,6-diepithio-3,4-di-O-methyl-1,2:5,6-tetradeoxy-D-mannitol (41),121,122 -L-iditol (42),122 and -Lallitol(43) 124. …”

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Cyclopolymerizations: Synthetic Tools for the Precision Synthesis of Macromolecular Architectures

2018

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“…[1][2][3][4][5][6][7][8] In particular, regio-and stereoselective cyclizations of dianhydro sugars, such as 1,2:5,6-dianhydrohexitols and 1,2:4,5-dianhydropentitols, are an interesting approach for the stereocontrolled synthesis of carbohydrate derivatives. [9][10][11][12][13][14][15][16] For example, Kuszmann reported that the regio-and stereoselective cyclizations of 3,4-di-O-alkyl-1,2:5,6-dianhydro-D D-mannitol and 3,4-di-O-alkyl-1,2:5,6-dianhydro-L L-iditol with hydrogen bromide produced the corresponding 2,5-anhydro-6-bromo-6-deoxy-D D-glucitol and 2,5-anhydro-1-bromo-1-deoxy-D D-glucitol, respectively. 9 In addition, we reported that the asymmetric cyclization of meso-1,2:5,6-dianhydrohexitols and meso-1,2:4,5-dianhydropentitols using chiral (salen)Co III Ac ((R,R)-1 and (S,S)-1) led to chiral anhydroalditol alcohols in extremely high enantiomeric excesses.…”

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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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Bulk cyclopolymerization of 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐1,2:5,6‐tetradeoxy‐D‐mannitol with quaternary ammonium salts leading to gel‐free thiosugar polymer

Satoh

Imai

Sugie

et al. 2002

J. Polym. Sci. A Polym. Chem.

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The bulk cyclopolymerization of diepisulfide, 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐1,2:5,6‐tetradeoxy‐D‐mannitol (1), was studied using R4N+Br− (R = CH3, C2H5, C3H7, C4H9, and C7H15) and (C4H9)4N+X− (X = Cl, I, NO3, and ClO4) as the initiators. All the bulk polymerizations of 1 using quaternary tetraalkylammonium salts at 90 °C proceeded without gelation even at high conversion to produce gel‐free polymers consisting of 2,5‐anhydro‐1,5‐dithio‐D‐glucitol (I) as the major cyclic repeating unit along with 1,5‐anhydro‐2,5‐dithio‐D‐mannitol (II) and the desulfurized acyclic unit (III) as the minor units. The polymerization rate and molar fraction of the I unit increased with the increasing alkyl chain length of the tetraalkylammonium cation and the increasing nucleophilicity of the counteranion. Tetrabutylammonium chloride exhibited the highest catalytic activity and the highest stereoselectivity, that is, the thiosugar polymer with I:II:III = 81:15:4 and a number‐average molecular weight of 31.9 × 103 was obtained in 85% yield for a polymerization time of 0.5 h. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 965–970, 2002

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Cyclopolymerization of 1,2:5,6-Diepithio-3,4- di-O-methyl-1,2,5,6-tetradeoxy-d-mannitol and -l-iditol Leading to a Novel Thiosugar Polymer

Cited by 7 publications

References 28 publications

Cyclopolymerizations: Synthetic Tools for the Precision Synthesis of Macromolecular Architectures

Cyclopolymerizations: Synthetic Tools for the Precision Synthesis of Macromolecular Architectures

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

Bulk cyclopolymerization of 1,2:5,6‐diepithio‐3,4‐di‐O‐methyl‐1,2:5,6‐tetradeoxy‐D‐mannitol with quaternary ammonium salts leading to gel‐free thiosugar polymer

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