Unique properties of the 11-cis and 11,11′-di-cis isomers of β-carotene as revealed by electronic absorption, resonance Raman and ¹H and ¹³C NMR spectroscopy and by HPLC analysis of their thermal isomerization

Abstract

In comparison with the all-trans and other cis isomers of β-carotene, the 11-cis and 11,11′-di-cis isomers exhibited the following unique properties. (1) The wavelengths of the B_u⁺â†�A_g^– (0–0) absorption of these two isomers are similar to that of the all-trans isomer, and do not follow the general rule of its blue shift found in other mono-cis and di-cis isomers. Their extinction coefficients are significantly lower than those of other isomers. (2) The frequencies of the C[double bond, length half m-dash]C stretching Raman lines of these isomers are the same as that of the all-trans isomer, and do not follow the general trend of high-frequency shifts found in other mono-cis and di-cis isomers. The Raman lines due to the out-of-plane C–H wagging and methyl rocking modes appear in the 11,11′-di-cis isomer. (3) The ¹H chemical shifts of these isomers indicate severe steric interaction between the methyl and the olefinic ¹H atoms in the concave side of the 11-cis bend, whereas their ¹³C chemical shifts suggest twisting and polarization of the cis C11[double bond, length half m-dash]C12 bond. (4) The rates of thermal isomerization of these isomers are much higher than that of the 15-cis isomer, i.e. the least stable isomer previously known.

The results lead us to the conclusion that the 11-cis configuration has inherent twisting around the double and single bonds in the cis bend due to the severe steric interaction between the 13-methyl and the 10-olefinic hydrogens, and that it is unstable enough to disappear thermally at room temperature.

References

1. Y. Koyama, J. Photochem. Photobiol. B: Biol., 1991, 9, 265.
2. Y. Koyama and Y. Mukai, Biomolecular Spectroscopy Part B, Advances in Spectroscopy, ed. R. J. H. Clark and R. E. Hester, Wiley, New York, 1993, vol. 8, p. 49.
3. N. Ohashi, N. Ko-chi, M. Kuki, T. Shimamura, R. J. Cogdell and Y. Koyama, Biospectrosc., 1996, 2, 59.
4. G. E. Bialek-Bylka, T. Tomo, K. Satoh and Y. Koyama, FEBS Lett., 1995, 363, 137.
5. G. E. Bialek-Bylka, T. Hiyama, K. Yumoto and Y. Koyama, Photosynth. Res., 1996, 49, 245.
6. T. Yoshizawa and G. Wald, Nature, 1963, 197, 1279.
7. R. S. Becker, Photochem. Photobiol., 1988, 48, 369.
8. L. Zechmeister, Cis-Trans Isomeric Carotenoids, Vitamins A, and Arylpolyenes, Academic Press, New York, 1962.
9. M. Denny and R. S. H. Liu, J. Am. Chem. Soc., 1977, 99, 4865.
10. (a) K. Tsukida, A. Kodama and M. Ito, J. Chromatogr., 1977, 134, 331; (b) V. Ramamurthy, M. Denny and R. S. H. Liu, Tetrahedron Lett., 1981, 22, 2463.
11. K. Tsukida and K. Saiki, J. Nutr. Sci. Vitaminol., 1982, 28, 311.
12. H. Hashimoto, Y. Miki, M. Kuki, T. Shimamura, H. Utsumi and Y. Koyama, J. Am. Chem. Soc., 1993, 115, 9216.
13. Y. Hu, A. Okumura, Y. Koyama, Y. Yamano and M. Ito, Spectrochim. Acta Part A, 1997, 53, 913.
14. Y. Mukai, Y. Koyama, M. Ito and K. Tsukida, J. Raman Spectrosc., 1986, 17, 387.
15. Y. Hu, T. Mizoguchi, Y. Kurimoto and Y. Koyama, Spectrochim. Acta Part A, 1995, 51, 1949.
16. K. Tsukida, K. Saiki, T. Takii and T. Koyama, J. Chromatogr., 1982, 245, 359.
17. Y. Koyama, T. Takii, K. Saiki and K. Tsukida, Photobiochem. Photobiophys., 1983, 5, 139.
18. Y. Koyama, I. Takatsuka, M. Nakata and M. Tasumi, J. Raman Spectrosc., 1988, 19, 37.
19. Y. Koyama, M. Hosomi, H. Hashimoto and T. Shimamura, J. Mol. Struct., 1989, 193, 185.
20. M. Kuki, Y. Koyama and H. Nagae, J. Phys. Chem., 1991, 95, 7171.
21. W. von E. Doering, C. Sotiriou-Leventis and W. R. Roth, J. Am. Chem. Soc., 1995, 117, 2747.
22. Y. Koyama, M. Hosomi, A. Miyata, H. Hashimoto, S. A. Reames, K. Nagayama, T. Kato-Jippo and T. Shimamura, J. Chromatogr., 1988, 439, 417.
23. S. Saito and M. Tasumi, J. Raman Spectrosc., 1983, 14, 310.
24. K. Iwata, H. Hayashi and M. Tasumi, Biochim. Biophys. Acta, 1985, 810, 269.
25. (a) H. Günther, NMR Spectroscopy 2nd edn., Wiley, Chichester, 1992; (b) E. Breitmaier and W. Voelter, Carbon-13 NMR Spectroscopy 3rd edn., VCH Verlag, Weinheim, 1987.
26. (a) M. C. Bruni, J. P. Daudey, J. Langlet, J. P. Malrieu and F. Momicchioli, J. Am. Chem. Soc., 1977, 99, 3587; (b) V. Bonačić-Koutecký and S. Ishimaru, J. Am. Chem. Soc., 1977, 99, 8134; (c) M. Aoyagi, Y. Osamura and S. Iwata, J. Chem. Phys., 1985, 83, 1140.
27. K. J. Laidler and H. Eyring, The Theory of Rate Processes, McGraw-Hill, New York, 1964.
28. I. Agalidis, M. Lutz and F. Reiss-Husson, Biochim. Biophys. Acta, 1980, 589, 264.
29. (a) H. Hopf and N. Krause, Tetrahedron Lett., 1985, 26, 3323; (b) P. A. Bütikofer and C. H. Eugster, Helv. Chim. Acta, 1983, 66, 1148; (c) J.-L. Olivé, M. Mousseron-Canet and J. Dornand, Bull. Soc. Chim. Fr., 1969, 3247.
30. V. L. Khristoforov, E. N. Zvonkova, V. P. Varlamov, O. N. Sorokina and R. P. Evstigneeva, J. Org. Chem. USSR (Engl. Transl.), 1973, 9, 1868; Zh. Org. Khim., 1973, 9, 1844.
31. (a) A. Furuhata, H. Yokokawa and M. Matsui, Agric. Biol. Chem., 1984, 48, 3129; (b) A. Nürrenbach, J. Paust, H. Pommer, J. Schneider and B. Schulz, Liebigs Ann. Chem., 1977, 1146.
32. O. Isler, L. H. Chopard-dit-Jean, M. Montavon, R. Rüegg and P. Zeller, Helv. Chim. Acta, 1957, 40, 1256.
33. J. D. Surmatis, US Patent 3 367 985, 1966; Chem. Abstr., 1968, 68, 114 786.
34. U. Burkert and N. L. Allinger, Molecular Mechanics, ACS Monograph 177, American Chemical Society, Washington DC, 1982.