Synthesis and oxidative transformations of 5-hydroxy-5α-cholest-8-en-3β-yl acetate
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Mihailović, Milhailo Lj.Dabović, Milan
Pavlović, Vladimir D.
Krstić, Natalija

Lorenc, Ljubinka
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5-Hydroxy-5α-cholest-8-en-3β-yl acetate (8) (prepared in 6 steps starting from 7-dehydrocholesteryl acetate (1) was transformed with ruthenium tetroxide to 5-hydroxy-8,9-dioxo-8,9-seco-5α-cholestan-3β-yl acetate (9). Treatment of the latter 8,9-seco-5-hydroxy derivative with lead tetraacetate (LTA) or mercuric oxide/iodine reagent (HgO/I2) resulted, instead of the expected oxidative β-fragmentation of its C(5)-C(10) bond, in the competing non-regio and non-stereoselective acetoxylation of the α-positions next to the 8- and 9-oxo functions (with LTA), and in the ≈ 82% recovery of the starting material (with HgO/I2). The results are discussed in terms of the strong hydrogen bonding which exists between the 5α-hydroxyl and the 8-oxo group.
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Lactones / Acetates / secosteroidal macrocyclesSource:
Journal of the Serbian Chemical Society, 1997, 62, 9, 719-726Publisher:
- Serbian Chemical Society
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IHTMTY - JOUR AU - Mihailović, Milhailo Lj. AU - Dabović, Milan AU - Pavlović, Vladimir D. AU - Krstić, Natalija AU - Lorenc, Ljubinka PY - 1997 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/2707 AB - 5-Hydroxy-5α-cholest-8-en-3β-yl acetate (8) (prepared in 6 steps starting from 7-dehydrocholesteryl acetate (1) was transformed with ruthenium tetroxide to 5-hydroxy-8,9-dioxo-8,9-seco-5α-cholestan-3β-yl acetate (9). Treatment of the latter 8,9-seco-5-hydroxy derivative with lead tetraacetate (LTA) or mercuric oxide/iodine reagent (HgO/I2) resulted, instead of the expected oxidative β-fragmentation of its C(5)-C(10) bond, in the competing non-regio and non-stereoselective acetoxylation of the α-positions next to the 8- and 9-oxo functions (with LTA), and in the ≈ 82% recovery of the starting material (with HgO/I2). The results are discussed in terms of the strong hydrogen bonding which exists between the 5α-hydroxyl and the 8-oxo group. PB - Serbian Chemical Society T2 - Journal of the Serbian Chemical Society T1 - Synthesis and oxidative transformations of 5-hydroxy-5α-cholest-8-en-3β-yl acetate VL - 62 IS - 9 SP - 719 EP - 726 UR - https://hdl.handle.net/21.15107/rcub_cer_2707 ER -
@article{ author = "Mihailović, Milhailo Lj. and Dabović, Milan and Pavlović, Vladimir D. and Krstić, Natalija and Lorenc, Ljubinka", year = "1997", abstract = "5-Hydroxy-5α-cholest-8-en-3β-yl acetate (8) (prepared in 6 steps starting from 7-dehydrocholesteryl acetate (1) was transformed with ruthenium tetroxide to 5-hydroxy-8,9-dioxo-8,9-seco-5α-cholestan-3β-yl acetate (9). Treatment of the latter 8,9-seco-5-hydroxy derivative with lead tetraacetate (LTA) or mercuric oxide/iodine reagent (HgO/I2) resulted, instead of the expected oxidative β-fragmentation of its C(5)-C(10) bond, in the competing non-regio and non-stereoselective acetoxylation of the α-positions next to the 8- and 9-oxo functions (with LTA), and in the ≈ 82% recovery of the starting material (with HgO/I2). The results are discussed in terms of the strong hydrogen bonding which exists between the 5α-hydroxyl and the 8-oxo group.", publisher = "Serbian Chemical Society", journal = "Journal of the Serbian Chemical Society", title = "Synthesis and oxidative transformations of 5-hydroxy-5α-cholest-8-en-3β-yl acetate", volume = "62", number = "9", pages = "719-726", url = "https://hdl.handle.net/21.15107/rcub_cer_2707" }
Mihailović, M. Lj., Dabović, M., Pavlović, V. D., Krstić, N.,& Lorenc, L.. (1997). Synthesis and oxidative transformations of 5-hydroxy-5α-cholest-8-en-3β-yl acetate. in Journal of the Serbian Chemical Society Serbian Chemical Society., 62(9), 719-726. https://hdl.handle.net/21.15107/rcub_cer_2707
Mihailović ML, Dabović M, Pavlović VD, Krstić N, Lorenc L. Synthesis and oxidative transformations of 5-hydroxy-5α-cholest-8-en-3β-yl acetate. in Journal of the Serbian Chemical Society. 1997;62(9):719-726. https://hdl.handle.net/21.15107/rcub_cer_2707 .
Mihailović, Milhailo Lj., Dabović, Milan, Pavlović, Vladimir D., Krstić, Natalija, Lorenc, Ljubinka, "Synthesis and oxidative transformations of 5-hydroxy-5α-cholest-8-en-3β-yl acetate" in Journal of the Serbian Chemical Society, 62, no. 9 (1997):719-726, https://hdl.handle.net/21.15107/rcub_cer_2707 .