Abstract
The association constants (K) of complexes of chiral neutral amines with optically active crown ethers ((S,S)-1, (S,S)-2, (S,S)-4 and (S,S)-5) which contain the phenyl chiral barriers and the phenol moiety bearing an additional para-substituent were determined at various temperatures by the1H n.m.r. spectroscopic method in CDCl3. The thermodynamic parameters for complexation, which were determined from the van’t Hoff plots of the K values, suggested that the acidity of the phenolic crown ethers markedly affected the enthalpy and entropy changes upon complexation with neutral amines. The crown ethers ((S,S)-2, (S,S)-4 and (S,S)-5) having higher acidity showed more negative ΔH and ΔS values and a larger slope in the enthalpy-entropy compensation plot than crown ether (S,S)-1 having a lower acidity. The temperature-dependent enantioselectivity in complexation of chiral neutral amines with (S,S,S,S)-6 containing phenyl substituents and the cyclohexane moieties as chiral barriers together with the p-(2,4-dinitrophenylazo)phenol moiety was also examined, demonstrating that steric interactions between the bulky steric barriers and the amine induced larger conformational changes of the host and guest molecules upon complexation. The data of the temperature-dependent enantioselectivity demonstrate a reversal of the relative merits of the enantioselectivity depending upon the temperature. A linear relatioship between the TΔR,SΔS values and the ΔR,SΔH values (TΔR,SΔS=0.812ΔR,SΔH-0.342, R=0.983) shows that the ΔR,SΔH and ΔR,SΔS values compensate each other. Therefore, complexation having a larger ΔR,SΔH value does not always show a higher degree of the enantioselectivity at any temperature than that having a smaller ΔR,SΔH value.
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References
J. D. Morrison and H. S. Mosher, “Asymmetric Organic Reactions”, Prentice-Hall, Englewood Cliffs, 1971
J. Retey and J. A. Robinson, “A Stereospecificity in Organic Chemistry and Enzymology”, Verlag Chemie, Weinheim, 1982
J. D. Morison (ed.), “Asymmetric Synthesis”, Vols. 1-5, Academic, New York, 1983-1984
G. M. Coppola and H. F. Schuster (ed.) “Asymmetric Synthesis”, Wiley-Interscience, New York, 1987.
K. Watabe, R. Charles and E. Gil-Av, Angew. Chem. Int. Ed. Engl., 28, 192 (1989)
V. Schurig, J. Ossig and R. Link, Angew. Chem. Int. Ed. Engl., 28, 194 (1989).
Van T. Pham, R. S. Phillips and L. G. Ljungdahl, J. Am. Chem. Soc., 111, 1935 (1989).
Y. Inoue, T. Yokoyama, M. Yamasaki and A. Tai, Nature [London], 341, 225 (1989).
K. Naemura, J. Fuji, K. Ogasahara, K. Hirose and Y. Tobe, J. Chem. Soc., Chem. Commun., 1996, 2749
K. Naemura, T. Wakebe, K. Hirose and Y. Tobe, Tetrahedron: Asymm., 8, 2585 (1997).
D. J. Cram, R. C. Helgeson, L. R. Sousa, J. M. Timko, M. Newcomb, P. Moreau, F. de Jong, G. W. Gokel, D. H. Hoffman, L. A. Domeier, S. C. Peacock, K. Madan and L. Kaplan, Pure Appl. Chem., 43, 327 (1975)
J. F. Stoddart, in “Progress in Macrocyclic Chemistry”, ed. R. M. Izatt and J. J. Christensen, John Wiely & Sons, New York, 1981
J. F. Stoddart, in “Topics in Stereochemistry”, ed. E. L. Eliel and S. H. Wilen, Vol. 17, John Wiely & Sons, New York, 1987
D. J. Cram, Angew. Chem. Int. Ed. Engl., 27, 1009 (1988)
R. M. Izatt, C. Y. Zhu, P. Huszthy and J. S. Bradshaw, in “Crown Compounds: Toward Future Applications”, ed. S. R. Cooper, VCH Publishers, New York, 1992
J. S. Bradshaw, P. Huszthy, C. W. McDaniel, M. Oue, C. Y. Zhu and R. M. Izatt, J. Coord. Chem., 27, 105 (1992)
T. Kaneda, in “Crown Ethers and Analogous Compounds”, ed. M. Hiraoka, Elsevier, Amsterdam, 1992
W. C. Still, Acc. Chem. Res., 29, 155 (1996)
T. H. Webb and C. S. Wilcox, Chem. Soc. Rev., 22, 38 (1993)
K. Naemura, Y. Tobe and T. Kaneda, Coord. Chem. Rev., 148, 199 (1996).
G. Dotsevi, Y. Sogah and D. J. Cram, J. Am. Chem. Soc., 98, 3038 (1976)
T. Shinbo, T. Yamaguchi, K. Nishimura and M. Sugiura, J. Chromatogr., 405, 145 (1987)
A. Shibukawa, in “Chiral Separations by HPLC”, ed. A. M. Krstulovic, Ellis Horwood, Chichester, 1989
D. W. Armstrong, Y. Tang, S. Chen, Y. Zhou, C. Bagwill and J.-R. Chen, Anal. Chem., 66, 1473 (1994).
K. Naemura, Y. Nishikawa, J. Fuji, K. Hirose and Y. Tobe, Tetrahedron: Asymm., 8, 873 (1997).
K. Naemura, K. Ueno, S. Takeuchi, K. Hirose, Y. Tobe, T. Kaneda and Y. Sakata, J. Chem. Soc., Perkin Trans. 1, 1996, 383.
D. B. Smithurd, T. B. Wyman and F. Diederich, J. Am. Chem. Soc., 113, 5420 (1991)
Y. Inoue and T. Hakushi, J. Chem. Soc., Perkin Trans. 2, 1985, 935
Y. Inoue, F. Amano, H. Inada, M. Ouchi, A. Tai, T. Hakushi, Y. Liu and L.-H. Tong, J. Chem. Soc., Perkin Trans. 2, 1990, 1239
Y. Inoue, T. Hakushi, Y. Liu, L.-H. Tong, B.-J. Shen and D.-S. Jin, J. Am. Chem. Soc., 115, 475 (1993).
T. Kaneda, Y. Ishizaki and S. Misumi, J. Am. Chem. Soc., 110, 2970 (1988)
T. Kaneda, K. Hirose and S. Misumi, J. Am. Chem. Soc., 111, 742 (1989).
K. Hirose, J. Fuji, K. Kamada, Y. Tobe and K. Naemura, J. Chem. Soc., Perkin Trans. 2, 1997, 1649
K. Ogasahara, K. Hirose, Y. Tobe and K. Naemura, J. Chem. Soc., Perkin Trans. 1, in press.
K. Naemura, K. Ueno, S. Takeuchi, Y. Tobe, T. Kaneda and Y. Sakata, J. Am. Chem. Soc., 115, 8475 (1993).
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Naemura, K., Matsunaga, K., Fuji, J. et al. Temperature Dependence of Enantioselectivity in Complexations of Optically Active Phenolic Crown Ethers with Chiral Amines in Solution. ANAL. SCI. 14, 175–182 (1998). https://doi.org/10.2116/analsci.14.175
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DOI: https://doi.org/10.2116/analsci.14.175