Abstract
Asymmetric anionic homopolymerization of N-4′-benzo 15-crown-5 maleimide (B15C5MI) was carried out with a chiral anionic initiator consisting of organometal (n-butyllithium, diethylzinc (Et2Zn)) and chiral ligand ((–)-sparteine ((–)-Sp), (S, S)-(1-ethylpropylidene)-bis(4-benzyl-2-oxazoline) ((S, S)-Bnbox)) to obtain optically active polymers. The polymer obtained with the chiral ligand had an optical rotation, suggesting that asymmetric induction occurred on the main chain of the polymer. Poly(B15C5MI) obtained with Et2Zn/(S, S)-Bnbox in tetrahydrofuran showed the highest specific rotation of −64.1°. The chiroptical properties and structures of the polymers obtained were analyzed by circular dichroism, ultraviolet, nuclear magnetic resonance and gel permeation chromatography measurements. The effects of adding (R)-cyclohexylethylamine to the obtained poly(B15C5MI) were investigated.
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References
Okamoto, Y., Suzuki, K., Ohta, K., Hatada, K. & Yuki, H. Optically active poly(triphenylmethyl methacrylate) with one-handed helical conformation. J. Am. Chem. Soc. 101, 4763 (1979).
Okamoto, Y., Suzuki, K. & Yuki, H. Asymmetric polymerization of triphenylmethyl methacrylate by optically active anionic catalysts. J. Polym. Sci. Polym. Chem. Ed. 18, 3043 (1980).
Nakano, T., Okamoto, Y. & Hatada, K. Asymmetric polymerization of triphenylmethyl methacrylate leading to a one-handed helical polymer: mechanism of polymerization. J. Am. Chem. Soc. 114, 1318 (1992).
Okamoto, Y. & Nakano, T. Asymmetric polymerization. Chem. Rev. 94, 349 (1994).
Oishi, T., Yamasaki, H. & Fujimoto, M. Asymmetric polymerization of N-substituted maleimides. Polym. J. 23, 759 (1991).
Oishi, T., Sase, K., Saeki, K., Yao, S. & Ohdan, K. Polymerization and copolymerization of N-cyclododecylmaleimide. Polymer 36, 3935 (1995).
Oishi, T., Onimura, K., Isobe, Y., Yanagihara, H. & Tsutsumi, H. Asymmetric anionic polymerization of maleimides bearing bulky substituents. J. Polym. Sci., Part A: Polym. Chem. 38, 310 (2000).
Zhou, H., Onimura, K., Tsutsumi, H. & Oishi, T. Synthesis and chiroptical properties of (S)-(-)-N-α-methylbenzylmaleimide polymers containing crystallinity. Polym. J. 33, 227 (2001).
Isobe, Y., Onimura, K., Tsutsumi, H. & Oishi, T. Asymmetric anionic polymerization of N-1-naphthylmaleimide with chiral ligand-organometal complexes in toluene. J. Polym. Sci., Part A: Polym. Chem. 39, 3556 (2001).
Isobe, Y., Onimura, K., Tsutsumi, H. & Oishi, T. Asymmetric polymerization of N-1-naphthylmaleimide with chiral anionic initiator: preparation of highly optically active poly(N-1-naphthylmaleimide). Macromolecules 34, 7617 (2001).
Isobe, Y., Onimura, K., Tsutsumi, H. & Oishi, T. Asymmetric polymerization of N-1-anthrylmaleimide with diethylzinc-chiral ligand complexes and optical resolution using the polymer. Polym. J. 34, 18 (2002).
Onimura, K., Zhang, Y., Yagyu, M. & Oishi, T. Asymmetric anionic polymerization of optically active N-1-cyclohexylethylmaleimide. J. Polym. Sci., Part A: Polym. Chem. 42, 4682 (2004).
Gao, H., Isobe, Y., Onimura, K. & Oishi, T. Asymmetric polymerization of (S)-N-maleoyl-L-leucine allyl ester and chiral recognition ability of its polymer as chiral stationary phase for HPLC. Polym. J. 39, 764 (2007).
Oishi, T., Gao, H., Nakamura, T., Isobe, Y. & Onimura, K. Asymmetric polymerizations of N-substituted maleimides bearing L-leucine ester derivatives and chiral recognition abilities of their polymers. Polym. J. 39, 1047 (2007).
Gao, H., Isobe, Y., Onimura, K. & Oishi, T. Synthesis and asymmetric polymerization of (S)-N-maleoyl-L-leucine propargyl ester. J. Polym. Sci., Part A: Polym. Chem. 45, 3722 (2007).
Cubbon, R. C. P. Free radical and anionic polymerization of some N-substituted maleimides. Polymer 6, 419 (1965).
Nonokawa, R. & Yashima, E. Detection and amplification of a small enantiomeric imbalance in α-amino acids by a helical poly(phenylacetylene) with crown ether pendants. J. Am. Chem. Soc. 125, 1278 (2003).
Nonokawa, R., Oodo, M. & Yashima, E. Helicity induction on a poly(phenylacetylene) derivative bearing Aza-15-crown-5 ether pendants in organic solvents and water. Macromolcules 36, 6599 (2003).
Morino, K., Oobo, M. & Yashima, E. Helicity induction in a poly(phenylacetylene) bearing Aza-18-crown-6 ether pendants with optically active bis(amino acid)s and its chiral stimuli-responsive gelation. Macromolcules 38, 3461 (2005).
Nonokawa, R. & Yashima, E. Helicity induction on a poly(phenylacetylene) derivative bearing Aza-18-crown-6 ether pendants in water. J. Polym. Sci., Part A: Polym. Chem. 41, 1004 (2003).
Morino, K., Kaptein, B. & Yashima, E. Detection of the chirality of Cα-methylated α-amino acids with a dynamic helical poly(phenylacetylene) Bearing Aza-18-crown-6 ether pendants. Chirality 18, 717 (2006).
Sakai, R., Satoh, T., Kakuchi, R., Kaga, H. & Kakuchi, T. Macromolecular helicity induction for novel optically inactive poly(phenyl isocyanate) bearing crown ether based on the host-guest complexation. Macromolecules 36, 3709 (2003).
Sakai, R., Satoh, T., Kakuchi, R., Kaga, H. & Kakuchi, T. Helicity induction of polyisocyanate with a crown cavity on the main chain synthesized by cyclopolymerization of α,ω-diisocyanate. Macromolecules 37, 3996 (2004).
Sakai, R., Otsuka, I., Satoh, T., Kakuchi, R., Kaga, H. & Kakuchi, T. Thermoresponsive on-off switching of chiroptical property induced in poly(4′-ethynylbenzo-15-crown-5)/α-amino acid system. Macromolecules 39, 4032 (2006).
Sakai, R., Otsuka, I., Satoh, T., Kakuchi, R., Kaga, H. & Kakuchi, T. Chiral discrimination of a helically organized crown ether array parallel to the helix axis of polyisocyanate. J. Polym. Sci., Part A: Polym. Chem. 44, 325 (2006).
Denmark, S. E., Nakajima, N. & Nicaise, O. J.- C. Asymmetric addition of organolithium reagents to imines. J. Am. Chem. Soc. 125, 1278 (2003).
Denmark, S. E., Nakajima, N., Nicaise, O. J.- C., Faucher, A.- M. & Edwards, J. P. Preparation of chiral bisoxazolines: observations on the effect of substituents. J. Org. Chem. 60, 4884 (1995).
Denmark, S. E., Stavenger, R. A., Faucher, A.- M. & Edwards, J. P. Cyclopropanation with diazomethane and Bis(oxazoline)palladium(II) complexes. J. Org. Chem. 62, 3375 (1997).
Reddy, P. Y., Kondo, S., Toru, T. & Ueno, Y. Lewis acid and hexamethyldisilazane-promoted efficient synthesis of N-Alkyl- and N-arylimide derivatives. J. Org. Chem. 62, 2652 (1997).
Reddy, P. Y., Kondo, S., Fujita, S. & Toru, T. Efficient synthesis of fluorophore-linked maleimide derivatives. Synthesis 1998, 999 (1998).
Onimura, K., Tsutsumi, H. & Oishi, T. Asymmetric anionic polymerization of N-substituted maleimides with Et2Zn and chiral bisoxazolines. Chem. Lett. 27, 791 (1998).
Onimura, K., Tsutsumi, H. & Oishi, T. Asymmetric polymerization of N-substituted maleimides with organolithium-bisoxazolines complexes. Polym. Bull. 39, 437 (1997).
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Azechi, M., Yamabuki, K., Onimura, K. et al. Asymmetric anionic polymerization of maleimide bearing an N-4′-benzo 15-crown-5 ether with an organometal/chiral ligand complex. Polym J 42, 632–639 (2010). https://doi.org/10.1038/pj.2010.54
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DOI: https://doi.org/10.1038/pj.2010.54
