Abstract
Chiral (S)-(−)-N-α-methylbenzylmaleimide ((S)-(−)-MBZMI) was polymerized with chiral complexes of (−)-sparteine (Sp) or (S,S)-(1-ethylpropylidene)bis(4-benzyl-2-oxazoline) (Bnbox) with organometal in toluene or tetrahydrofuran (THF). Specific rotations [α]43525 of the polymers obtained by Et2Zn/Sp and Et2Zn/Bnbox were +20.5° to +466.2° and +9.4° to +39.5°, respectively. In the asymmetric anionic polymerization of (S)-(−)-MBZMI, Sp was found a more effective chiral ligand than Bnbox. Chirality of the polymers was mainly attributed to different ratios between stereogenic centers (S,S) and (R,R) in the main chain produced by asymmetric induction. Crystalline poly((S)-(−)MBZMI)s obtained with Et2Zn/Sp at lower temperatures in toluene having specific rotations [α]43525 more than +200° showed higher stereoregularity, compared to that of poly((R)-(+)-MBZMI) under the same conditions, judging from X-Ray diffraction diagrams and 13C NMR spectra. Chiroptical properties of these polymers may partially be due to helical conformation.
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Zhou, H., Onimura, K., Tsutsumi, H. et al. Synthesis and Chiroptical Properties of (S)-(−)-N-α-Methylbenzylmaleimide Polymers Containing Crystallinity. Polym J 33, 227–235 (2001). https://doi.org/10.1295/polymj.33.227
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DOI: https://doi.org/10.1295/polymj.33.227
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