Abstract
The structure and absolute configuration of naturally occurring Carnosol have been investigated by X-ray analyses. Crystal data are: orthorhombic P21212;a=15.762(1),b=13.755(1),c=7.7747(7) Å,Z=4,V=1688.2 Å3, andR=0.031 (2569 reflections). The absolute configuration is established at a significance level better than 0.995 according to HamiltonsR-factor test and is in accordance with that predicted experimentally by chemically means. Correlation of the solid-state IR pattern of the regions sensitive to hydrogen bonding (CO and OH stretching bands) with the X-ray crystal structure is excellent and shows, that even weak inter- and intramolecular hydrogen bonds may be unambiguously identified by IR spectroscopy. The variable-temperature nuclear magnetic resonance studies (NMR) show that the twinning of the signals from the isopropyl methyl protons cannot be due to hindered rotation but can be ascribed magnetic nonequivalence induced by the chiral centers.
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References
Aldrich Library of Infrared Spectra (1985) Spectrum No. 13501–1.
Applications of Dynamic NMR Spectroscopy to Organic Chemistry (1985), Michinori Oki, ed. (VCH Publisher, Fla).
Asao, M., Iwamura, H., Akamatsu, M., and Fujita, T. (1987)J. Med. Chem. 1873–79.
Bellamy, L. J. (1975)The Infra-red Spectra of Complex Molecules (Methuen and Co., London).
Bellamy, L. J. (1968)Advances in Infrared Group Frequencies (Methuen and Co., London).
Blessing, R. H. (1987)Cryst. Rev. 1, 3–58.
Brieskorn, C. H., and Fuchs, A. (1962)Chem. Ber. 95, 3034–41.
Brieskom, C. H., Fuchs, A., Bredenberg, J. B., McChesney, J. D., and Wenkert, E. (1964)J. ORG. CHEM. 29, 2293–98.
Cañigueral, S., Iglesias, J., Sanchez-Ferrando, F., and Virgili, A. (1988)Phytochem.27, 221–24.
Cromer, D. T., and Mann, J. B. (1968)Acta Cryst. A 24, 321–4.
Cromer, D. T., and Liberman, D. J. (1970)J. Chem. Phys. 53, 1891–98.
Encarnacion, R. D., Keer, S. G., Nielsen, P. H., and Christophersen, C. (1990)J. Ethnopharmacol. Submitted for publication.
Fraga, B. M., Gonzalez, A. G., Herrera, J. R., Luis, J. G., Perales, A., and Ravelo, A. G. (1985)Phytochem. 24, 1853–54.
Fraga, B. M., Gonzalez, A. G., Herrera, J. R., Luis, J. G., and Ravelo, A. G. (1986)Phytochem. 25, 269–71.
Inatani, R., Nakatani, N., Fuwa, H., and Seto, H. (1982)Agric. Biol. Chem. 46, 1661–6.
Ingraham, L. L., Corse, J., Bailey, G. F., and Stitt, F. (1952)J. Am. Chem. Soc. 74, 2297–99.
International Tables for X-Ray Crystallography (1974)Vol. IV (Kynoch Press, Birmingham), pp. 287–93.
Jennings, W. B. (1975)Chem. Rev. 75, 307–22.
Kelecom, A. (1983)Tetrahedron 39, 3603–07.
Kelecom, A., and Medeiros, W. L. B. (1987)Quim. Nova 10, 153.
Kelecom, A., Santos, T. C. D., and Medeiros, W. L. B. (1986)Ann. Acad. Brasil. Cienc. 58, 53–59.
Kuchita, T., and Kubo, I. (1969)Nature (London) 223, 97–99.
Kuhn, L. P., and Bowman, R. E. (1961)Spectrochim. Acta 17, 650–60.
Kumazawa, T., Nomura, T., and Kurihara, K. (1988)Biochemistry 27, 1239–44.
Lee, C.-H. (1987)Adv. Carbohydr. Chem. Biochem. 45, 199–349.
Linde, H. (1964)Helv. Chim. Acta 47, 1234–1239.
Meyer, W. L., Manning, R. A., Schroeder, R. S., and Shew, D. C. (1976)J. Org. Chem. 41, 1005–15.
Nyquist, R. A. (1963)Spectrochim. Acta 19, 1655–64.
Oki, M. (1985) Applications of Dynamic NMR Spectroscopy to Organic Chemistry. (VCH Verlagsgesellschaft, Weinheim), pp. 199–204.
Pinto, A. C., Patitucci, M. L., Zocher, D. H. T., and Kelecom, A. (1985)Phytochem. 24, 2345–47.
Rogers, D. (1981)Acta Cryst. A 37, 734–41.
Seguin, J.-P., Guillaume-Vilport, F., Uzan, R., and Doucet, J.-P. (1986)J. Chem. Soc. Perkin 2, 773–9.
Sheldrick, G. M. (1985) inCrystallographic Computing Vol. 3 (Oxford University Press).
Stewart, R. F., Davidson, E. R., and Simpson, W. T. (1965)J. Chem. Phys. 42, 3175–87.
Structure Determination Package (1981) (Enraf Nonius Delft, Holland).
Wu, J. W., Lee, M.-H., Ho, C.-T., and Chang, S. S. (1982)JAOCS 59, 339–45.
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Gajhede, M., Anthoni, U., Per Nielsen, H. et al. Carnosol. Crystal structure, absolute configuration, and spectroscopic properties of a diterpene. Journal of Crystallographic and Spectroscopic Research 20, 165–171 (1990). https://doi.org/10.1007/BF01160970
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DOI: https://doi.org/10.1007/BF01160970