Anionic polymerization of monomers containing functional groups. 4. Anionic living polymerization of N,N-dialkyl-4-vinylbenzenesulfonamides

Ishizone, Takashi; Tsuchiya, Junji; Hirao, Akira; Nakahama, Seiichi

doi:10.1021/ma00045a002

Cited by 40 publications

(36 citation statements)

References 9 publications

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“…52 4-Vinylbenzenesulfonyl chloride (5) was prepared from sodium 4-styrenesulfonate and thionyl chloride. 53 Crosslinked Polystyrene-Supported N-Sulfonylated b-Amino Alcohol Resin 4…”

Section: Methodsmentioning

confidence: 99%

Polystyrene‐supported N‐sulfonylated amino alcohols and their applications to titanium(IV) complexes catalyzed enantioselective diethylzinc additions to aldehydes

Hui¹,

Chen²,

Wu³

et al. 2006

Chirality

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Crosslinked polystyrene-supported resins 4, 7a, and 7b containing N-sulfonylated beta-amino alcohol in 98, 20, and 40% loadings are prepared. Asymmetric diethylzinc additions to benzaldehyde employing titanium complexes of 10 mol % resins 4, 7a, or 7b are examined and the best performed 7a/Ti(O-i-Pr)4 catalytic system applies to various aldehydes to afford desired secondary alcohols in excellent enantioselectivities up to 95% ee. The resin 7a is reused five times, giving the product with enantioselectivities >or=86% ee and an 81% ee is obtained when the resin is used the sixth time. The used resin 7a is refreshed with 1 M HCl and the asymmetric reaction employing the regenerated resin 7a gives the product in 88% ee.

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“…52 4-Vinylbenzenesulfonyl chloride (5) was prepared from sodium 4-styrenesulfonate and thionyl chloride. 53 Crosslinked Polystyrene-Supported N-Sulfonylated b-Amino Alcohol Resin 4…”

Section: Methodsmentioning

confidence: 99%

Polystyrene‐supported N‐sulfonylated amino alcohols and their applications to titanium(IV) complexes catalyzed enantioselective diethylzinc additions to aldehydes

Hui¹,

Chen²,

Wu³

et al. 2006

Chirality

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“…We have recently realized anionic living polymerization of a series of styrene derivatives containing electronwithdrawing groups 1) such as N,N-dialkylamide 2) , Nalkylimine 3) , N-arylimine 4) , trimethylsilylethynyl 5) , alkylethynyl 6) , oxazoline 7) , N,N-dialkylsulfonamide 8) , and cyano groups 9) . The polymerization of these monomers quantitatively afforded the polymers having predicted molecular weights and narrow molecular weight distribu-tions (MWDs).…”

Section: Introductionmentioning

confidence: 99%

Anionic polymerization of monomers containing functional groups, 14. Anionic polymerizations of aryl 4-vinylbenzoates

Ishizone

Katô

Hirao

et al. 2000

Macromol. Chem. Phys.

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Anionic polymerizations of phenyl (2a), 4‐methoxyphenyl (2b), 2‐methylphenyl (2c), 2‐tert‐butylphenyl (2d), 3,5‐di‐tert‐butylphenyl (2e), 2,6‐dimethylphenyl (1f), 2,6‐diisopropylphenyl (2g), 2,6‐di‐tert‐butyl‐4‐methylphenyl (2h), and 2,6‐di‐tert‐butyl‐4‐methoxyphenyl (2i) 4‐vinylbenzoates were carried out in THF at –78°C with diphenylmethylpotassium and oligo(α‐methylstyryl)lithium and ‐dipotassium. No apparent polymerizations of 2a–2e occurred probably due to the inherent side reactions such as nucleophilic attack of the anionic initiators toward the ester carbonyl groups. On the other hand, the polymerizations of 2f–2i, the monomers possessing bulky aryl ester substituents, certainly proceeded to afford the polymers in quantitative yields. The molecular weight distribution (MWD) of poly(2f) was broad (Mw/Mn = 1.3–1.8), indicating partial side reactions during the course of the polymerization. By contrast, the resulting poly(2g–2i) possessed narrow MWDs (Mw/Mn = 1.1) and predicted molecular weights based on the molar ratios between monomers to initiators. It was thus demonstrated that the steric hindrance around the ester carbonyl group was essential to obtain polymers having well‐defined chain structures via controlled anionic polymerizations of aryl 4‐vinylbenzoates. Novel tailored block copolymers, polyisoprene‐block‐poly(2h), poly(2h)‐block‐polystyrene‐block‐poly(2h), poly(tert‐butyl methacrylate)‐block‐poly(2h), and poly(2h)‐block‐poly(2‐isopropenylbenzoxazole) were synthesized by the sequential copolymerization of 2h and the corresponding comonomers. It was elucidated from the results of block copolymerization that anionic polymerizability of 2h was apparently higher than that of styrene because of the electron‐withdrawing effect of the COOAr substituent.

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“…Methacrylic acid and methyl methacrylate were distilled under reduced pressure. p ‐Styrenesulfonyl chloride was prepared according to the method reported in the literature . Monomer 3i (2‐methacryloyloxyethyl phosphorylcholine) was supplied from NOF Corporation, Japan.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of chiral iridium complexes immobilized on amphiphilic polymers and their application to asymmetric catalysis

Itsuno

Hashimoto

Haraguchi

2014

J. Polym. Sci. Part A: Polym. Chem.

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This article details the enantioselective catalytic performance of crosslinked, polymer immobilized, Ir-based, chiral complexes for transfer hydrogenation of cyclic imines to chiral amines. Polymerization of the achiral vinyl monomer, divinylbenzene, and a polymerizable chiral 1,2-diamine monosulfonamide ligand followed by complexation with [IrCl 2 Cp*] 2 affords the crosslinked polymeric chiral complex, which can be successfully applied to asymmetric transfer hydrogenation of cyclic imines. Polymeric catalysts prepared from amphiphilic achiral monomers have high catalytic activity in the reaction and can be used both in organic solvents and water to give chiral cyclic amines with a high level of enantioselectivity (up to 98% ee). The asymmetric reaction allows for reuse of the heterogeneous catalyst without any loss in activity or enantioselectivity over several runs.

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Anionic polymerization of monomers containing functional groups. 4. Anionic living polymerization of N,N-dialkyl-4-vinylbenzenesulfonamides

Cited by 40 publications

References 9 publications

Polystyrene‐supported N‐sulfonylated amino alcohols and their applications to titanium(IV) complexes catalyzed enantioselective diethylzinc additions to aldehydes

Polystyrene‐supported N‐sulfonylated amino alcohols and their applications to titanium(IV) complexes catalyzed enantioselective diethylzinc additions to aldehydes

Anionic polymerization of monomers containing functional groups, 14. Anionic polymerizations of aryl 4-vinylbenzoates

Synthesis of chiral iridium complexes immobilized on amphiphilic polymers and their application to asymmetric catalysis

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