Asymmetric Polymerization of N-Substituted Maleimide

Oishi, Tsutomu; Yamasaki, Hiroko; Fujimoto, Minoru

doi:10.1295/polymj.23.795

Cited by 94 publications

(59 citation statements)

References 12 publications

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“…This is consistent with the fact that optically active RMI homopolymers obtained from asymmetric polymerization of achiral RMI with n-butyllithium (n-BuLi)/( -)-sparteine indicated characteristic CD peaks at 250 nm. 10 Therefore, it is considered that CD peaks in the vicinity of 240 to 270 nm and for the MBCM copolymers may be associated with the threo-diisotactic structure of maleimide. Asymmetric polymerizations of achiral RMI gave optically active RMI polymers having relatively high specific rotation (CHMI:…”

Section: Optical Behavior Of the Copolymersmentioning

confidence: 99%

Asymmetric Induction Copolymerization of Chiral N-[N′-(α-Methylbenzyl)aminocarbonylmethyl]maleimide with Achiral N-(Substituted)maleimide

Oishi

Kagawa

Fujimoto

1993

Polym J

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Section: Optical Behavior Of the Copolymersmentioning

confidence: 99%

Asymmetric Induction Copolymerization of Chiral N-[N′-(α-Methylbenzyl)aminocarbonylmethyl]maleimide with Achiral N-(Substituted)maleimide

Oishi

Kagawa

Fujimoto

1993

Polym J

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“…11 In the report, N-cyclohexyl maleimide polymer showed larger specific rotation ([a] 0 ) and Cotton effect than other RMI polymers. This suggests that bulkiness of N-substituent may be advantageous for asymmetric polymerization and asymmetric induction polymerization.…”

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confidence: 94%

Polymerizability and Chiroptical Properties of the N-Substituted Maleimide Bearing L-Phenylalanine Alkyl Ester

Kagawa

Oishi

1996

Polym J

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ABSTRACT:Four types of N-maleoyl-L-phenylalaninc alkyl ester (RPAM) polymers were synthesized from maleic anhydride, L-phenylalanine and the corresponding alcohols, i.e., ethyl, butyl, dodecyl, or benzyl alcohol. Radical and anionic polymerizations were performed. Bulkiness of the ester group decreased polymerizability. However, bulkiness was favorable to asymmetric induction into the homopolymer main chain. In addition, polymers obtained by radical polymerizations had regular main chain structures smaller than those obtained by anionic polymerizations. The difference of the regularity caused different chiroptical properties of the polymers. Radical copolymerizations with styrene (ST) or methyl methacrylate (MMA) were performed and monomer reactivity ratios and Alfrey-Price Q-e were determined. Chiroptical properties of the copolymers were significantly influenced by the ST or MMA ca-unit. Bulkiness of the ester group hardly influenced chiroptical properties of the copolymers.KEY WORDS Asymmetric Induction / Asymmetric Perturbation / N-Substituted Maleimide / Styrene / Methyl Methacrylatc / L-Phenylalanine Ester / Optically Active Polymer / We reported polymerizations of N-substituted maleimide (RMI) bearing optically active groups. 1 -10 In the reports, the polymers obtained showed asymmetric induction in the main chain and asymmetric perturbation in the side chain chromophore. Since RMI has a pentagonal plane structure with a polymerizable double bond and a pair of imide chromophores exhibiting the n--+n* transition, there is large possibility of asymmetric induction and asymmetric perturbation. In the recent systematic studies of optically active RMI, 5 • 9 chiroptical properties of poly(RMI) were significantly influenced by the location of the chiral carbon in the side chain. That is, the shorter the distance between the imide ring and chiral carbon, the greater the influence for chirality of the polymer.On the other hand, we reported asymmetric polymerization of achiral N-alkyl maleimides with n-butyllithium/( -)-sparteine and optical activity of the resulting polymers. 11 In the report, N-cyclohexyl maleimide polymer showed larger specific rotation ([a] 0 ) and Cotton effect than other RMI polymers. This suggests that bulkiness of N-substituent may be advantageous for asymmetric polymerization and asymmetric induction polymerization.Recently, we reported polymerizations and copolymerizations of RMI bearing L-amino acid, i.e., L-phenyl alanine, L-alanine, 8 or its cyclohexyl ester(CHPAM). 10 Chiroptical properties of poly(CHPAM) exhibited significant differences between poly(CHPAM) and the corresponding model compound in chiroptical property. This is mostly attributable to the influence of the location of a chiral carbon in N-substituent. However, the influence of the bulkiness of ester group is not found yet. The objective of our investigation is to explore whether bulkiness of the ester group in N-substituent affects polymerizabilities and chiroptical properties of the polymers and the copolymers. The fi...

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“…As shown in Figure 1(a), an isotactic polymer thus produced possesses a mirror plane, if we ignore both its secondary structure (e.g., helicity) 5,6 and the small difference between the two chain ends (pseudo-chirality). Accordingly, only a limited number of reports have appeared on the asymmetric synthesis of an optically active polymer from an achiral monomer through the control of the newly created chirotopic centers apart from helical chirality; 7,8 examples include the asymmetric polymerization of alkyl sorbate, 9,10 maleimide, 11,12 and epoxide or episulfide. 13,14 The synthesis of a helical polymer through the control of its plus or minus helicity has been the major interest in this area.…”

Section: Chirality In Polymer Synthesismentioning

confidence: 99%