Chirality induction arising from the twist of template on the cyclocopolymerization of 2,3‐<i>O</i>‐isopropylidene‐1,4‐di‐<i>O</i>‐methacryloyl‐<scp>L</scp>‐threitol with styrene

Yokota, Kazuaki; Kakuchi, Toyoji; Sakurai, Ko‐ichi; Iwata, Yoji; Kawai, Hiroki

doi:10.1002/marc.1992.030130702

Cited by 13 publications

(7 citation statements)

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“…The cyclocopolymerization of 2,3- O -isopropylidene-1,4-di- O -methacryloyl- l -threitol with styrene yielded poly(methacrylic acid- co -styrene) which became optically active with an increasing fraction of comonomer units .…”

Section: Introductionmentioning

confidence: 99%

“…1 Wulff et al synthetically realized the chirality induction during the cyclocopolymerization of the chiral bifunctional monomers, bis(4-vinylphenyl)boronate [2][3][4][5][6] and bis [4-[(methacryloyl)oxy]phenyl]boronate 7 carrying a 3,4-O-cyclohexylidene-D-mannitol template, with achiral monomers. We have also reported the cyclocopolymerization of dimethacrylate 8 and bis(4-vinylbenzoate) [9][10][11][12][13][14] having saccharide moieties with styrene to yield optically active poly(methyl methacrylate-co-styrene) and poly(methyl 4-vinylbenzoate-co-styrene).…”

Section: Introductionmentioning

confidence: 99%

“…The cyclocopolymerization of 2,3-O-isopropylidene-1,4di-O-methacryloyl-L-threitol with styrene yielded poly-(methacrylic acid-co-styrene) which became optically active with an increasing fraction of comonomer units. 8 The bis(4-vinylbenzoate) monomers were useful for determining the absolute configuration of the cyclic units using the exciton chirality method. 9 The chirality of dibenzoate showed the configurational change in the polymerization process, and thus the template transmitted its chirality to the main chain during the intramolecular cyclization to form an enantiomeric cyclic unit.…”

Section: Introductionmentioning

confidence: 99%

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Chirality Induction in Cyclopolymerization. 8. Cyclocopolymerization of 1,2:5,6-Di-O-isopropylidene- 3,4-di-O-methacryloyl-d-mannitol with Styrene

1997

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Radical cyclocopolymerization of the dimethacrylate 1 (M1), which was derived from 1,2:5,6-di-O-isopropylidene-d-mannitol, with styrene (M2) induced new chirality in the polymer chain. The removal of the chiral template in the copolymer 2 followed by treatment with diazomethane gave optically active poly(methyl methacrylate-co-styrene) (4). Polymer 4 had more active chirality upon increasing the M1 unit, thus indicating that the new chirality should be induced by the M1 diad unit rather than the isolated M1 unit. Characteristics of monomer 1 include the considerably higher fraction of tactic triad rr in poly(methyl methacrylate) (PMMA) derived from the homopolymerization and the larger probability of forming the racemo diad of the M1 unit during the intermolecular reaction of the copolymerization. In polymer 4, the origin of chirality was assigned to the chiral tetrad sequences of the MMA unit which were induced by participation of the racemo configuration.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chirality Induction in Cyclopolymerization. 8. Cyclocopolymerization of 1,2:5,6-Di-O-isopropylidene- 3,4-di-O-methacryloyl-d-mannitol with Styrene

1997

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“…The cyclocopolymerization of the divinyl monomer containing a chiral template with a monovinyl comonomer, followed by removing the template, is one certain method of synthesizing an optically active vinyl polymer. − Therefore, it is necessary to examine various chiral compounds and to determine their efficiency as a template for asymmetric induction. Carbohydrate is one of the useful sources for the cyclocopolymerization method.…”

Section: Introductionmentioning

confidence: 99%

Chirality Induction in Cyclopolymerization. 2. Synthesis of Optically Active Poly[(methyl 4-vinylbenzoate)-co-styrene] by Cyclocopolymerization of 1,2:5,6-Di-O-isopropylidene-3,4-bis-O-(4-vinylbenzoyl)-d-mannitol and -d-glucitol with Styrene

et al. 1996

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1,2:5,6-Di-O-isopropylidene-3,4-bis-O-(4-vinylbenzoyl)-d-mannitol (1a) and -d-glucitol (1b) with styrene (St) were polymerized using AIBN in toluene at 60 °C to yield copolymers (2a and 2b, respectively) consisting essentially of the cyclic repeating and styrene units. In order to confirm asymmetric induction in 2, the removal of the template from 2 was carried out using KOH in aqueous MeOH, and then the resulting hydrolyzed copolymer was treated with diazomethane for conversion into poly[(methyl 4-vinylbenzoate)-co-styrene] (3). Copolymers 2a and 2b showed a negative specific rotation, whereas a positive rotation was observed for 3a and 3b. The CD spectrum of 1a exhibited a negative Cotton effect at 300.0 nm and a positive one at 267.3 nm as well as a negative exciton coupling of 1b. According to the exciton chirality method, 1a and 1b had a negative chirality and its benzoate chromophores, the two 4-vinylbenzoyl groups, were twisted counterclockwise. On the other hand, the CD spectrum of 3a (1a/St = 0.30/0.70) and 3b (1b/St = 0.27/0.73) showed a split Cotton effect with a positive one at 254.9 nm and a negative one at 237.1 nm for 3a and with a positive Cotton effect at 254.7 nm and a negative one at 232.7 nm for 3b. This result indicated that 3 had a positive chirality in which two 4-vinylbenzoyl groups were twisted clockwise, i.e., the vicinal (methyl 4-vinylbenzoate) groups in the main chain were an (S,S)-configuration.

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“…The optical activity was ascribed to chiral ( S , S ) -diad units generated in the polymer chain through the cyclopolymerization step [139] . Other different bifunctional monomers such as 85 [140] , 86 [141] , 87 [142] , and 88 [143] have been reported to promote this type of copolymerization with styrene.…”

Section: Methacrylatesmentioning

confidence: 99%

Asymmetric Polymerization

Ito¹,

Nozaki²

2010

Catalytic Asymmetric Synthesis

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Chirality induction arising from the twist of template on the cyclocopolymerization of 2,3‐O‐isopropylidene‐1,4‐di‐O‐methacryloyl‐L‐threitol with styrene

Cited by 13 publications

References 13 publications

Chirality Induction in Cyclopolymerization. 8. Cyclocopolymerization of 1,2:5,6-Di-O-isopropylidene- 3,4-di-O-methacryloyl-d-mannitol with Styrene

Chirality Induction in Cyclopolymerization. 8. Cyclocopolymerization of 1,2:5,6-Di-O-isopropylidene- 3,4-di-O-methacryloyl-d-mannitol with Styrene

Chirality Induction in Cyclopolymerization. 2. Synthesis of Optically Active Poly[(methyl 4-vinylbenzoate)-co-styrene] by Cyclocopolymerization of 1,2:5,6-Di-O-isopropylidene-3,4-bis-O-(4-vinylbenzoyl)-d-mannitol and -d-glucitol with Styrene

Asymmetric Polymerization

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