Abstract
(S)-N-Maleoyl-L-leucine allyl ester ((S)-ALMI), a kind of N-substituted maleimide having two double bonds with different reactivities, was newly synthesized from maleic anhydride, L-leucine, and allyl alcohol. Asymmetric polymerizations were carried out to obtain optically active polymers. Poly((S)-ALMI) obtained by anionic polymerization with n-butyllithium/(S,S)-(1-ethylpropylidene)-bis(4-benzyl-2-oxazoline) (n-BuLi/Bnbox) complex in THF showed the highest negative specific rotation of −429.1°. Chemoselective polymerization behaviors of (S)-ALMI on the two reactive groups were elucidated. In anionic polymerizations, only the double bond in the maleimide moiety exclusively took part in the polymerization, affording the corresponding poly((S)-ALMI) with the allyl pendant group. In radical polymerizations, the solvents strongly affect the radical polymerization behaviors of (S)-ALMI. Chiroptical properties and structures of the poly((S)-ALMI)s obtained were investigated by GPC, CD, XRD, and NMR measurements. The methods of preparing chiral stationary phases (CSPs) for high performance liquid chromatography (HPLC) and the chiral recognition ability of the optically active poly((S)-ALMI) were also discussed.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Y. Okamoto and T. Nakano, Chem. Rev., 94, 349 (1994).
T. Yasuzawa, H. Yamaguchi, and Y. Minoura, J. Polym. Sci., Polym. Chem. Ed., 17, 3387 (1979).
K. Ohta, Y. Okamoto, K. Hatada, and H. Yuki, J. Polym. Sci., Polym. Chem. Ed., 17, 2917 (1979).
H. Yuki, Y. Okamoto, and I. Okamoto, J. Am. Chem. Soc., 102, 6356 (1980).
C. G. Overberger, C. X. Lu, and C. C. Chen, J. Polym. Sci., Part A: Polym. Chem., 24, 75 (1986).
E. Yashima, C. Yamamoto, and Y. Okamoto, Synlett, 1998, 344 (1998).
T. Takata, Y. Furusho, K. Murakawa, T. Endo, H. Mastuoka, Y. Hirasa, J. Mastuo, and M. Sisido, J. Am. Chem. Soc., 120, 4530 (1998).
T. Oishi, K. Onimura, W. Sumida, T. Koyanagi, and H. Tsutsumi, Polym. Bull., 48, 317 (2002).
T. Oishi, H. Yamasaki, and M. Fujimoto, Polym. J., 23, 795 (1991).
T. Oishi, K. Matsusaki, and M. Fujimoto, Polym. J., 24, 1281 (1992).
T. Oishi, Y. Otsubo, and M. Fujimoto, Polym. J., 24, 527 (1992).
K. Kagawa and T. Oishi, Polym. J., 27, 579 (1995).
T. Oishi, H. Nagata, and H. Tsutsumi, Polymer, 39, 4135 (1998).
K. Onimura, H. Tsutsumi, and T. Oishi, Macromolecules, 31, 5971 (1998).
K. Onimura, H. Tsutsumi, and T. Oishi, Chem. Lett., 27, 791 (1998).
T. Oishi, K. Onimura, K. Tanaka, W. Horimoto, and H. Tsutsumi, J. Polym. Sci., Part A: Polym. Chem., 37, 473 (1999).
H. Zhou, K. Onimura, H. Tsutsumi, and T. Oishi, Polym. J., 32, 552 (2000).
H. Zhou, K. Onimura, H. Tsutsumi, and T. Oishi, Polym. J., 33, 227 (2001).
Y. Isobe, K. Onimura, H. Tsutsumi, and T. Oishi, Macromolecules, 34, 7617 (2001).
Y. Isobe, K. Onimura, H. Tsutsumi, and T. Oishi, J. Polym. Sci., Part A: Polym. Chem., 39, 3556 (2001).
T. Oishi, K. Onimura, Y. Isobe, and H. Tsutsumi, Chem. Lett., 28, 673 (1999).
Y. Isobe, K. Onimura, H. Tsutsumi, and T. Oishi, Polym. J., 34, 18 (2002).
T. Oishi, Y. Isobe, K. Onimura, and H. Tsutsumi, Polym. J., 35, 245 (2003).
Y. Zhang, K. Onimura, H. Tsutsumi, and T. Oishi, Polym. J., 36, 878 (2004).
K. Onimura, Y. Zhang, M. Yagyu, and T. Oishi, J. Polym. Sci., Part A: Polym. Chem., 42, 4682 (2004).
T. Oishi, Y. Zhang, T. Fukushima, and K. Onimura, Polym. J., 37, 453 (2005).
K. Kagawa and T. Oishi, Polym. J., 28, 1 (1996).
R. C. P. Cubbon, Polymer, 6, 419 (1965).
T. Oishi and K. Onimura, Kobunshi Ronbunshu, 59, 287 (2002).
G. M. Coppola and H. F. Schuster, “Asymmetric Synthesis: Construction of Chiral Molecules Using Amino Acids,” John Wiley & Sons, Inc., New York, N. Y., 1987.
G. Gao, F. Sanda, and T. Masuda, Macromolecules, 36, 3932 (2003).
M. Mennicken, R. Nagelsdiek, H. Keul, and H. Höcker, Macromol. Chem. Phys., 205, 2429 (2004).
T. Hagiwara, I. Suzuki, K. Takeuchi, H. Hamana, and T. Narita, Macromolecules, 24, 6856 (1991).
M. Rubin, T. Schwier, and V. Gevorgyan, J. Org. Chem., 67, 1936 (2002).
I. W. Muderawan, T. T. Ong, and S. C. Ng, J. Sep. Sci., 29, 1849 (2006).
H. Gao, Y. Isobe, K. Onimura, and T. Oishi, Polym. J., 38, 1288 (2006).
H. Gao, Y. Isobe, K. Onimura, and T. Oishi, J. Polym. Sci., Part A: Polym. Chem., in press.
S. E. Denmark, N. Nakajima, O. J.-C. Nicaise, A.-M. Faucher, and J. P. J. Edwards, J. Org. Chem., 60, 4884 (1995).
T. Oishi, K. Onimura, H. Yanagihara, and H. Tsutsumi, J. Polym. Sci., Part A: Polym. Chem., 38, 310 (2000).
Y. Isobe, M. Nakamura, H. Gao, K. Onimura, and T. Oishi, Kobunshi Ronbunshu, 63, 484 (2006).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Gao, H., Isobe, Y., Onimura, K. et al. 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, 764–776 (2007). https://doi.org/10.1295/polymj.PJ2006231
Received:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1295/polymj.PJ2006231
Keywords
This article is cited by
-
Direct observation of cyclic poly(N-substituted maleimide)s with broad size distributions synthesized by anionic polymerization using an N-heterocyclic carbene and successive ring closure without high dilutions
Polymer Journal (2020)
-
Synthesis and characterization of optically active poly(phenylene-ethynylene)s containing chiral oxazoline derivatives
Polymer Journal (2012)
-
Asymmetric anionic polymerizations of N-substituted itaconimides having chiral amino-acid esters
Polymer Journal (2011)
-
Synthesis and asymmetric polymerization of chiral maleimides bearing an aza crown ether
Polymer Journal (2011)
-
Synthesis and properties of N-substituted maleimides conjugated with 1,4-phenylene or 2,5-thienylene polymers
Polymer Journal (2010)
