Abstract
Asymmetric anionic homopolymerizations of N-1-anthrylmaleimide (1-AMI) were performed with diethylzinc (Et2Zn)-chiral ligand complexes to obtain optically active polymers. The optical activity of poly(1-AMI) was influenced by polymerization conditions such as temperature, solvents and structures of chiral ligands. Poly(1-AMI) obtained with Et2Zn/(–)-2,2’-(1-ethylpropylidene)bis(4-benzyl-2-oxazoline) (Bnbox) in THF at 0°C showed the highest specific optical rotation ([α]D25=+92.5°). CD spectra of (+)-poly(1-AMI) exhibited negative exciton chirality around 230–300 nm, indicating that 1Bbtransition moments of anthryl groups were twisted counterclockwise. Chiral recognition ability of poly(1-AMI) was investigated by 1H NMR and HPLC, and the polymer coated on silica gel optically resolved 1, 1’-bi-2-naphthol.
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T. Oishi, H. Yamasaki, and M. Fujimoto, Polym. J., 23, 795 (1991).
K. Onimura, H. Tsutsumi, and T. Oishi, Polym. Bull., 39, 437 (1997).
K. Onimura, H. Tsutsumi, and T. Oishi, Macromolecules, 31, 5971 (1998).
K. Onimura, H. Tsutsumi, and T. Oishi, Chem. Lett., 791 (1998).
T. Oishi, K. Onimura, K. Tanaka, W. Horimoto, and H. Tsutsumi, J. Polym. Sci., Part A: Polym. Chem., 37, 473 (1999).
T. Oishi, K. Onimura, Y. Isobe, and H. Tsutsumi, Chem. Lett., 673 (1999).
T. Oishi, K. Onimura, Y. Isobe, H. Yanagihara, and H. Tsutsumi, J. Polym. Sci., Part A: Polym. Chem., 38, 310 (2000).
Y. Isobe, K. Onimura, H. Tsutsumi, and T. Oishi, Polym. J., 32, 1052 (2000).
Y. Isobe, K. Onimura, H. Tsutsumi, and T. Oishi, J. Polym. Sci., Part A: Polym. Chem., 39, 3556 (2001).
Y. Isobe, K. Onimura, H. Tsutsumi, and T. Oishi, Macromolecules, 34, 7617 (2001).
R. C. P. Cubbon, Polymer, 6, 419 (1965).
Y. Okamoto and T. Nakano, Chem. Rev., 94, 349 (1994).
T. Nakano, K. Taniguchi, and Y. Okamoto, Polym. J., 29, 540 (1997).
T. Nakano, Y. Hidaka, and Y. Okamoto, Polym. J., 30, 596 (1998).
T. Nakano, Y. Satoh, and Y. Okamoto, Polym. J., 30, 635 (1998).
J. Wu, T. Nakano, and Y. Okamoto, J. Polym. Sci., Part A: Polym. Chem., 36, 2013 (1998).
J. Wu, T. Nakano, and Y. Okamoto, J. Polym. Sci., Part A: Polym. Chem., 37, 2645 (1999).
Y. Okamoto and E. Yashima, Angew. Chem. Int. Ed., 37, 1020 (1998).
G. Hesse and R. Hagel, Chromatographia, 6, 277 (1973).
Y. Okamoto, M. Kawashima, K. Yamamoto, and K. Hatada, Chem. Lett., 739 (1984).
Y. Okamoto, M. Kawashima, and K. Hatada, J. Am. Chem. Soc., 106, 5357 (1984).
I. W. Wainer, M. C. Alembic, J. Chromatogr., 358, 85 (1986).
Y. Okamoto, M. Kawashima, and K. Hatada, J. Chromatogr., 363, 173 (1986).
Y. Okamoto, R. Aburatani, and K. Hatada, J. Chromatogr., 389, 95 (1987).
I. W. Wainer, R. M. Stiffin, and T. Shibata, J. Chromatogr., 411, 139 (1987).
Y. Okamoto, K. Hatano, R. Aburatani, and K. Hatada, Chem. Lett., 715 (1989).
N. Enomoto, S. Furukawa, Y. Ogasawara, H. Akano, Y. Kawamura, E. Yashima, and Y. Okamoto, Anal. Chem., 68, 2798 (1996).
P. Y. Reddy, S. Kondo, T. Toru, and Y. Ueno, J. Org. Chem., 62, 2652 (1997).
P. Y. Reddy, S. Kondo, S. Fujita, and T. Toru, Synthesis, 999 (1998).
A. Abiko and S. Masamune, Terrahedron Lett., 33, 5517 (1992).
S. E. Denmark, N. Nakajima, O. J.-C. Nicaise, A.-M. Faucher, and J. P. Edwards, J. Org. Chem., 60, 4884 (1995).
Y. Okamoto, M. Matsuda, T. Nakano, and E. Yashima, J. Polym. Sci., Part A: Polym. Chem., 32, 309 (1994).
K. Maeda and Y. Okamoto, Macromolecules, 31, 1046 (1998).
K. Maeda and Y. Okamoto, Macromolecules, 31, 5164 (1998).
N. Harada and K. Nakanishi, “Circular Dichroic Spectroscopy–Exciton Coupling in Organic Stereochemistry”, University Science Books, Sausalito, CA, 1983.
E. Yashima, C. Yamamoto, and Y. Okamoto, J. Am. Chem. Soc., 118, 4036 (1996).
K. Onimura, H. Tsutsumi, and T. Oishi, 10th Int. Symp. on Chiral Discrimination, Vienna, Aug. 30–Sep. 2, Abstracts, 1998, p 106.
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Isobe, Y., Onimura, K., Tsutsumi, H. et al. Asymmetric Polymerization of N-1-Anthrylmaleimide with Diethylzinc-Chiral Ligand Complexes and Optical Resolution Using the Polymer. Polym J 34, 18–24 (2002). https://doi.org/10.1295/polymj.34.18
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DOI: https://doi.org/10.1295/polymj.34.18
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