5-hydroxy-1-oxo-5α-cholestan-3β-yl acetate (11) was prepared in 5 steps starting from (E)-3β-acetoxy-5,10-seco-1(10)-cholesten-5-one (6). Treatment of the 1-oxo-5-hydroxy derivative 11 with lead tetraacetate (LTA) (under thermal or hypoiodite conditions) or with mercuric oxide/iodine (HgO/I2) reagent resulted in the oxidative β-fragmentation of the C(5)–C(10) bond affording 1,5-dioxo-5,10-secocholest-10(19)-en-3β-yl acetate (12), in different yields, depending on the reagent. Also the stereochemistry of the 1β,6β-cyclization product 13, formed by transannular cyclization of the 1,5-diketone 12 on silica gel, is discussed in this work.
Sintetizovan je 5-hidroksi-1-okso-5α-holestan-3β-il-acetata (11) u 5 faza polazeći od (E)- 3β-acetoksi-5,10-seko-1(10)-holesten-5-ona (6). Dejstvom olovo-tetraacetata (LTA) (pod termičkim ili hipojoditnim uslovima), ili merkuri-oksid/jodnog reagensa (HgO/I2) na 1-okso-5-hidroksi derivat 11, vrši se oksidativna β-fragmentacija njegove C(5)–C(10) veze, pri čemu se dobija 1,5-diokso-5,10-sekoholest-10(19)-en-3β-il-acetat (12), u različitim prinosima u zavisnosti od upotrebljenog reagensa. Takođe, diskutovana je stereohemija 1β,6β-ciklizacionog proizvoda 13, nastalog intramolekulskom ciklizacijom 1,5-diokso-5,10-seko jedinjenja 12 na silika gelu.
TY - JOUR
AU - Krstić, Natalija
AU - Bjelaković, Mira
AU - Lorenc, Ljubinka
AU - Pavlović, Vladimir D.
PY - 2003
UR - https://cer.ihtm.bg.ac.rs/handle/123456789/109
AB - 5-hydroxy-1-oxo-5α-cholestan-3β-yl acetate (11) was prepared in 5 steps starting from (E)-3β-acetoxy-5,10-seco-1(10)-cholesten-5-one (6). Treatment of the 1-oxo-5-hydroxy derivative 11 with lead tetraacetate (LTA) (under thermal or hypoiodite conditions) or with mercuric oxide/iodine (HgO/I2) reagent resulted in the oxidative β-fragmentation of the C(5)–C(10) bond affording 1,5-dioxo-5,10-secocholest-10(19)-en-3β-yl acetate (12), in different yields, depending on the reagent. Also the stereochemistry of the 1β,6β-cyclization product 13, formed by transannular cyclization of the 1,5-diketone 12 on silica gel, is discussed in this work.
AB - Sintetizovan je 5-hidroksi-1-okso-5α-holestan-3β-il-acetata (11) u 5 faza polazeći od (E)- 3β-acetoksi-5,10-seko-1(10)-holesten-5-ona (6). Dejstvom olovo-tetraacetata (LTA) (pod termičkim ili hipojoditnim uslovima), ili merkuri-oksid/jodnog reagensa (HgO/I2) na 1-okso-5-hidroksi derivat 11, vrši se oksidativna β-fragmentacija njegove C(5)–C(10) veze, pri čemu se dobija 1,5-diokso-5,10-sekoholest-10(19)-en-3β-il-acetat (12), u različitim prinosima u zavisnosti od upotrebljenog reagensa. Takođe, diskutovana je stereohemija 1β,6β-ciklizacionog proizvoda 13, nastalog intramolekulskom ciklizacijom 1,5-diokso-5,10-seko jedinjenja 12 na silika gelu.
PB - Serbian Chemical Society
T2 - Journal of the Serbian Chemical Society
T1 - Oxidative fragmentation of 5-hydroxy-1-oxo-5α-cholestan-3β-yl acetate
T1 - Oksidativne fragmentacije 5-hidroksi-1-okso-5α-holestan-3β-il-acetata
VL - 68
IS - 11
SP - 785
EP - 794
DO - 10.2298/JSC0311785K
ER -
@article{
author = "Krstić, Natalija and Bjelaković, Mira and Lorenc, Ljubinka and Pavlović, Vladimir D.",
year = "2003",
abstract = "5-hydroxy-1-oxo-5α-cholestan-3β-yl acetate (11) was prepared in 5 steps starting from (E)-3β-acetoxy-5,10-seco-1(10)-cholesten-5-one (6). Treatment of the 1-oxo-5-hydroxy derivative 11 with lead tetraacetate (LTA) (under thermal or hypoiodite conditions) or with mercuric oxide/iodine (HgO/I2) reagent resulted in the oxidative β-fragmentation of the C(5)–C(10) bond affording 1,5-dioxo-5,10-secocholest-10(19)-en-3β-yl acetate (12), in different yields, depending on the reagent. Also the stereochemistry of the 1β,6β-cyclization product 13, formed by transannular cyclization of the 1,5-diketone 12 on silica gel, is discussed in this work., Sintetizovan je 5-hidroksi-1-okso-5α-holestan-3β-il-acetata (11) u 5 faza polazeći od (E)- 3β-acetoksi-5,10-seko-1(10)-holesten-5-ona (6). Dejstvom olovo-tetraacetata (LTA) (pod termičkim ili hipojoditnim uslovima), ili merkuri-oksid/jodnog reagensa (HgO/I2) na 1-okso-5-hidroksi derivat 11, vrši se oksidativna β-fragmentacija njegove C(5)–C(10) veze, pri čemu se dobija 1,5-diokso-5,10-sekoholest-10(19)-en-3β-il-acetat (12), u različitim prinosima u zavisnosti od upotrebljenog reagensa. Takođe, diskutovana je stereohemija 1β,6β-ciklizacionog proizvoda 13, nastalog intramolekulskom ciklizacijom 1,5-diokso-5,10-seko jedinjenja 12 na silika gelu.",
publisher = "Serbian Chemical Society",
journal = "Journal of the Serbian Chemical Society",
title = "Oxidative fragmentation of 5-hydroxy-1-oxo-5α-cholestan-3β-yl acetate, Oksidativne fragmentacije 5-hidroksi-1-okso-5α-holestan-3β-il-acetata",
volume = "68",
number = "11",
pages = "785-794",
doi = "10.2298/JSC0311785K"
}
Krstić, N., Bjelaković, M., Lorenc, L.,& Pavlović, V. D.. (2003). Oxidative fragmentation of 5-hydroxy-1-oxo-5α-cholestan-3β-yl acetate. in Journal of the Serbian Chemical Society
Serbian Chemical Society., 68(11), 785-794.
https://doi.org/10.2298/JSC0311785K
Krstić N, Bjelaković M, Lorenc L, Pavlović VD. Oxidative fragmentation of 5-hydroxy-1-oxo-5α-cholestan-3β-yl acetate. in Journal of the Serbian Chemical Society. 2003;68(11):785-794.
doi:10.2298/JSC0311785K .
Krstić, Natalija, Bjelaković, Mira, Lorenc, Ljubinka, Pavlović, Vladimir D., "Oxidative fragmentation of 5-hydroxy-1-oxo-5α-cholestan-3β-yl acetate" in Journal of the Serbian Chemical Society, 68, no. 11 (2003):785-794,
https://doi.org/10.2298/JSC0311785K . .
