In this paper a synthetic pathway to the modified 5,10:13,14-bisfragmentation cholestane derivatives 8-14 is described. The synthesis involves introduction of the 5α- and 14α-hydroxyl groups in the cholestane molecule and subsequent cleavage of the C(5)-C(10) bond in 5α,14α-dihydroxycholestan-3β-yl acetate (4) with the HgO/I2 reagent and the C(13)-C(14) bond in the stereoisomeric 14α-hydroxy-5,10-secosteroids 5 and 6 with the Pb(OAc)4/I2 reagent. Complete and unambiguous 1H and 13C NMR resonance assignments of the obtained secosteroids, as well as the solution conformations of their 10- and 9-membered rings were determined by extensive analysis of 1D and 2D NMR spectral data. The structures and the solid-state conformations of 5,10-secosteroids 5-7 were confirmed by X-ray analysis. All diseco-compounds have a novel 5,10:13,14-disecocholestane skeleton.
TY - JOUR
AU - Bjelaković, Mira
AU - Krstić, Natalija
AU - Todorović, Nina
AU - Krunić, Aleksej
AU - Tinant, Bernard
AU - Dabović, Milan
AU - Pavlović, Vladimir D.
PY - 2009
UR - https://cer.ihtm.bg.ac.rs/handle/123456789/620
AB - In this paper a synthetic pathway to the modified 5,10:13,14-bisfragmentation cholestane derivatives 8-14 is described. The synthesis involves introduction of the 5α- and 14α-hydroxyl groups in the cholestane molecule and subsequent cleavage of the C(5)-C(10) bond in 5α,14α-dihydroxycholestan-3β-yl acetate (4) with the HgO/I2 reagent and the C(13)-C(14) bond in the stereoisomeric 14α-hydroxy-5,10-secosteroids 5 and 6 with the Pb(OAc)4/I2 reagent. Complete and unambiguous 1H and 13C NMR resonance assignments of the obtained secosteroids, as well as the solution conformations of their 10- and 9-membered rings were determined by extensive analysis of 1D and 2D NMR spectral data. The structures and the solid-state conformations of 5,10-secosteroids 5-7 were confirmed by X-ray analysis. All diseco-compounds have a novel 5,10:13,14-disecocholestane skeleton.
PB - Oxford : Pergamon-Elsevier Science Ltd
T2 - Tetrahedron
T1 - 5,10:13,14-Disecosteroids: novel modified steroids containing 10- and 9-membered rings
VL - 65
IS - 46
SP - 9557
EP - 9568
DO - 10.1016/j.tet.2009.09.066
ER -
@article{
author = "Bjelaković, Mira and Krstić, Natalija and Todorović, Nina and Krunić, Aleksej and Tinant, Bernard and Dabović, Milan and Pavlović, Vladimir D.",
year = "2009",
abstract = "In this paper a synthetic pathway to the modified 5,10:13,14-bisfragmentation cholestane derivatives 8-14 is described. The synthesis involves introduction of the 5α- and 14α-hydroxyl groups in the cholestane molecule and subsequent cleavage of the C(5)-C(10) bond in 5α,14α-dihydroxycholestan-3β-yl acetate (4) with the HgO/I2 reagent and the C(13)-C(14) bond in the stereoisomeric 14α-hydroxy-5,10-secosteroids 5 and 6 with the Pb(OAc)4/I2 reagent. Complete and unambiguous 1H and 13C NMR resonance assignments of the obtained secosteroids, as well as the solution conformations of their 10- and 9-membered rings were determined by extensive analysis of 1D and 2D NMR spectral data. The structures and the solid-state conformations of 5,10-secosteroids 5-7 were confirmed by X-ray analysis. All diseco-compounds have a novel 5,10:13,14-disecocholestane skeleton.",
publisher = "Oxford : Pergamon-Elsevier Science Ltd",
journal = "Tetrahedron",
title = "5,10:13,14-Disecosteroids: novel modified steroids containing 10- and 9-membered rings",
volume = "65",
number = "46",
pages = "9557-9568",
doi = "10.1016/j.tet.2009.09.066"
}
Bjelaković, M., Krstić, N., Todorović, N., Krunić, A., Tinant, B., Dabović, M.,& Pavlović, V. D.. (2009). 5,10:13,14-Disecosteroids: novel modified steroids containing 10- and 9-membered rings. in Tetrahedron
Oxford : Pergamon-Elsevier Science Ltd., 65(46), 9557-9568.
https://doi.org/10.1016/j.tet.2009.09.066
Bjelaković M, Krstić N, Todorović N, Krunić A, Tinant B, Dabović M, Pavlović VD. 5,10:13,14-Disecosteroids: novel modified steroids containing 10- and 9-membered rings. in Tetrahedron. 2009;65(46):9557-9568.
doi:10.1016/j.tet.2009.09.066 .
Bjelaković, Mira, Krstić, Natalija, Todorović, Nina, Krunić, Aleksej, Tinant, Bernard, Dabović, Milan, Pavlović, Vladimir D., "5,10:13,14-Disecosteroids: novel modified steroids containing 10- and 9-membered rings" in Tetrahedron, 65, no. 46 (2009):9557-9568,
https://doi.org/10.1016/j.tet.2009.09.066 . .
