Acid-catalyzed and photolytic reactivity of some unsaturated B-nor-5, 10-secosteroidal ketones
Kiselo-katalizovana i fotolitička reaktivnost nekih nezasićenih B-nor-5,10-sekosteroidnih ketona
Апстракт
The acid-catalyzed reaction of (Z)- and (E)-B-nor-5,10-seco-ketones 2 and 3 resulted in an intramolecular cyclization to give the 5-hydroxy-A-nor-1β,5β-10(19)-methylidene derivative 8, the 5β-hydroxy-A-nor-1(10)-unsaturated compound 9 and the 5β,10β-dihydroxy A-nor-product 10, from the (Z)-isomer and the 5-hydroxy-A-nor-1β,5β-10(19)-methylidene product 11, from the (E)-isomer. Upon UV-irradiation, the (Z)- and (E)-seco-ketones 2 and 3 underwent a reversible (Z)/(E) and (E)/(Z)-isomerization and in addition to a transannular photocyclization to afford the 10(19)-methylidene derivatives 8 and 11, respectively, while photolysis of the 10(19)-methylidene-B-nor-5,10-seco-ketone 4 gave the oxetane derivative 12.
Kiselo-katalizovana reakcija (Z)- i (E)-B-nor-5,10-seko-ketona 2 i 3 rezultuje u intramolekulskoj ciklizaciji dajući 5-hidroksi-A-nor-1β,5β-10(19)-metilidenski derivat 8, 5β-hidroksi A-nor-1(10)-nezasićeno jedinjenje 9 i 5β,10β-dihidroksi-A-nor-proizvod 10, iz Z-izomera, i 5-hidroksi-A-nor-1β,5β-10(19)-metilidenski proizvod 11, iz E-izomera. (Z)- i (E)-Seko- ketoni 2 i 3 UV-ozračivanjem podležu reverzibilnoj (Z)/(E) odnosno (E)/(Z) izomerizaciji, kao i transanularnoj fotociklizaciji dajući 10(19)-metilidenske derivate 8 odnosno 11, dok se fotolizom 10(19)-metilidenskog-5,10-seko-ketona 4 gradi oksetanski derivat 12.
Кључне речи:
(Z)- and (E)-B-nor-5,10-secosteroidal ketones / 10(19)-methylidene-B-nor-5,10-secosteroidal ketone / acid-catalyzed reactions / photolytic reactions / mechanistic interpretationИзвор:
Journal of the Serbian Chemical Society, 2003, 68, 4-5, 303-312Издавач:
- Serbian Chemical Society
DOI: 10.2298/JSC0305303B
ISSN: 0352-5139
WoS: 000183423800009
Scopus: 2-s2.0-0037835592
Институција/група
IHTMTY - JOUR AU - Bjelaković, Mira AU - Pavlović, Vladimir D. AU - Dabović, Milan AU - Lorenc, Ljubinka PY - 2003 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/115 AB - The acid-catalyzed reaction of (Z)- and (E)-B-nor-5,10-seco-ketones 2 and 3 resulted in an intramolecular cyclization to give the 5-hydroxy-A-nor-1β,5β-10(19)-methylidene derivative 8, the 5β-hydroxy-A-nor-1(10)-unsaturated compound 9 and the 5β,10β-dihydroxy A-nor-product 10, from the (Z)-isomer and the 5-hydroxy-A-nor-1β,5β-10(19)-methylidene product 11, from the (E)-isomer. Upon UV-irradiation, the (Z)- and (E)-seco-ketones 2 and 3 underwent a reversible (Z)/(E) and (E)/(Z)-isomerization and in addition to a transannular photocyclization to afford the 10(19)-methylidene derivatives 8 and 11, respectively, while photolysis of the 10(19)-methylidene-B-nor-5,10-seco-ketone 4 gave the oxetane derivative 12. AB - Kiselo-katalizovana reakcija (Z)- i (E)-B-nor-5,10-seko-ketona 2 i 3 rezultuje u intramolekulskoj ciklizaciji dajući 5-hidroksi-A-nor-1β,5β-10(19)-metilidenski derivat 8, 5β-hidroksi A-nor-1(10)-nezasićeno jedinjenje 9 i 5β,10β-dihidroksi-A-nor-proizvod 10, iz Z-izomera, i 5-hidroksi-A-nor-1β,5β-10(19)-metilidenski proizvod 11, iz E-izomera. (Z)- i (E)-Seko- ketoni 2 i 3 UV-ozračivanjem podležu reverzibilnoj (Z)/(E) odnosno (E)/(Z) izomerizaciji, kao i transanularnoj fotociklizaciji dajući 10(19)-metilidenske derivate 8 odnosno 11, dok se fotolizom 10(19)-metilidenskog-5,10-seko-ketona 4 gradi oksetanski derivat 12. PB - Serbian Chemical Society T2 - Journal of the Serbian Chemical Society T1 - Acid-catalyzed and photolytic reactivity of some unsaturated B-nor-5, 10-secosteroidal ketones T1 - Kiselo-katalizovana i fotolitička reaktivnost nekih nezasićenih B-nor-5,10-sekosteroidnih ketona VL - 68 IS - 4-5 SP - 303 EP - 312 DO - 10.2298/JSC0305303B ER -
@article{ author = "Bjelaković, Mira and Pavlović, Vladimir D. and Dabović, Milan and Lorenc, Ljubinka", year = "2003", abstract = "The acid-catalyzed reaction of (Z)- and (E)-B-nor-5,10-seco-ketones 2 and 3 resulted in an intramolecular cyclization to give the 5-hydroxy-A-nor-1β,5β-10(19)-methylidene derivative 8, the 5β-hydroxy-A-nor-1(10)-unsaturated compound 9 and the 5β,10β-dihydroxy A-nor-product 10, from the (Z)-isomer and the 5-hydroxy-A-nor-1β,5β-10(19)-methylidene product 11, from the (E)-isomer. Upon UV-irradiation, the (Z)- and (E)-seco-ketones 2 and 3 underwent a reversible (Z)/(E) and (E)/(Z)-isomerization and in addition to a transannular photocyclization to afford the 10(19)-methylidene derivatives 8 and 11, respectively, while photolysis of the 10(19)-methylidene-B-nor-5,10-seco-ketone 4 gave the oxetane derivative 12., Kiselo-katalizovana reakcija (Z)- i (E)-B-nor-5,10-seko-ketona 2 i 3 rezultuje u intramolekulskoj ciklizaciji dajući 5-hidroksi-A-nor-1β,5β-10(19)-metilidenski derivat 8, 5β-hidroksi A-nor-1(10)-nezasićeno jedinjenje 9 i 5β,10β-dihidroksi-A-nor-proizvod 10, iz Z-izomera, i 5-hidroksi-A-nor-1β,5β-10(19)-metilidenski proizvod 11, iz E-izomera. (Z)- i (E)-Seko- ketoni 2 i 3 UV-ozračivanjem podležu reverzibilnoj (Z)/(E) odnosno (E)/(Z) izomerizaciji, kao i transanularnoj fotociklizaciji dajući 10(19)-metilidenske derivate 8 odnosno 11, dok se fotolizom 10(19)-metilidenskog-5,10-seko-ketona 4 gradi oksetanski derivat 12.", publisher = "Serbian Chemical Society", journal = "Journal of the Serbian Chemical Society", title = "Acid-catalyzed and photolytic reactivity of some unsaturated B-nor-5, 10-secosteroidal ketones, Kiselo-katalizovana i fotolitička reaktivnost nekih nezasićenih B-nor-5,10-sekosteroidnih ketona", volume = "68", number = "4-5", pages = "303-312", doi = "10.2298/JSC0305303B" }
Bjelaković, M., Pavlović, V. D., Dabović, M.,& Lorenc, L.. (2003). Acid-catalyzed and photolytic reactivity of some unsaturated B-nor-5, 10-secosteroidal ketones. in Journal of the Serbian Chemical Society Serbian Chemical Society., 68(4-5), 303-312. https://doi.org/10.2298/JSC0305303B
Bjelaković M, Pavlović VD, Dabović M, Lorenc L. Acid-catalyzed and photolytic reactivity of some unsaturated B-nor-5, 10-secosteroidal ketones. in Journal of the Serbian Chemical Society. 2003;68(4-5):303-312. doi:10.2298/JSC0305303B .
Bjelaković, Mira, Pavlović, Vladimir D., Dabović, Milan, Lorenc, Ljubinka, "Acid-catalyzed and photolytic reactivity of some unsaturated B-nor-5, 10-secosteroidal ketones" in Journal of the Serbian Chemical Society, 68, no. 4-5 (2003):303-312, https://doi.org/10.2298/JSC0305303B . .