Abstract
The ground-state conformational analysis of previtamin D, its E-isomer, tachysterol, their 10-desmethyl analogues and 1-methyl-1-hydroxy-previtamins have been performed by force-field calculations. Differences in the absorption characteristics of these compounds are discussed in view of the chromophore geometry and abundance (%) of the calculated conformers according to a Boltzmann distribution at 298 K. On the basis of present calculations, the red shift of previtamin D low-temperature UV and CD spectra determined earlier is attributed to the shift of conformational equilibrium in favour of more stable cZc geometries. The effect of complex formation with simplest model cluster of silica surface ((H3SiO)3SiOH), on previtamin D and tachysterol conformational equilibria and on UV-absorbance maxima has been evaluated.
Similar content being viewed by others
References
H.J.C. Jacobs and E. Havinga, Adv. Photochem. 11, 305 (1979). b) F. Bernardi, M. Olivucci, I.N. Ragazos, and M.A. Robb, J. Am. Chem. Soc. 114, 8211 (1992).
O. Dmitrenko and W. Reischl, Monatshefte für Chemie 127, 445 (1996).
R. Wilbrandt and F.W. Langkilge. In: Structures and Conformations of Non-Rigid Molecules, J. Laane et al. (Eds.), Kluwer Academic Publishers, 1993, p. 567. b) U. Mazzucato and F. Momicchioli, Chem. Rev. 91, 1679 (1991).
R.B. Koolstra, J. Cornelisse, and H.J.C. Jacobs, Recl. Trav. Chim. Pays-Bas 106, 526 (1987).
H. Ishida, M. Shimizu, K. Yamamoto, Y. Iwasaki, and S. Yamada, J. Org. Chem. 60, 1828 (1995).
O.G. Perminova, Ph.D. Thesis, Kiev, 1990 (in Russian).
G MMX and PC-MODEL (Serena Software, Bloomington, Indiana) for SGI Indigo 2.-MMP2 (QCPE 395) for the IBM 3090 mainframe computer.-N.L. Allinger and H.L. Flanagan, J. Comput. Chem. 4, 399 (1983).
W.G. Dauben and D.J.H. Funhoff, J. Org. Chem. 53, 5070 (1988).
E.L. Eliel, N.L. Allinger, S.J. Angyal, and G.A. Morrison, Conformational Analysis, Interscience, New York, 1965, p. 102.
O. Hofer, H. Kählig, and W. Reischl, Monatshefte für Chemie 124, 185 (1993).
W. Klyne and V. Prelog, Exerientia 12, 521 (1960).
E. Berman, N. Friedman, Y. Mazur, M. Sheves, Z.V. Zaretskii, I. Proc. Workshop Vitam. D, 4th, 1979, 65.
P.A. Maessen, Ph.D. Thesis, Leiden, 1983.
J. Lugtenburg and E. Havinga, Tetrahedron Lett. 2391 (1969).
K.H. Pfoertner and M. Voelker, J. Chem. Soc. Perkin Trans. 2 527 (1991).
P.A. Maessen, H.J.C. Jacobs, J. Cornelisse, and E. Havinga, Angewandte Chemie 95, 752 (1983).
V. Malatesta, C. Willis, and P.A. Hackett, J. Am. Chem. Soc. 103, 6781 (1981).
I.B. Berlman, Phys. Chem. 74(16), 3085 (1970).
J. Sauer, P. Ugliengo, E. Garrone, and V.R. Saunders, Chem. Rev. 94, 2095 (1994).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Dmitrenko, O., Reischl, W. Ground-state conformational equilibrium of previtamin D and its E-isomer: Effect on the absorption characteristics. Res. Chem. Intermed. 23, 691–702 (1997). https://doi.org/10.1163/156856797X00484
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1163/156856797X00484