Photooxygenation of pregnanes
The course of the singlet-oxygen reaction with pregn-17(20)-enes and pregn-5,17(20)-dienes was studied to compare the reactivity of the two alkene moieties present in some steroid families. Thus, from commercially available (3β,5α)-hydroxy-androstan-17-one and (3β)-3-hydroxyandroxst-5- en-17-one, th...
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2004
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_0018019X_v87_n12_p2987_Ponce http://hdl.handle.net/20.500.12110/paper_0018019X_v87_n12_p2987_Ponce |
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paper:paper_0018019X_v87_n12_p2987_Ponce2023-06-08T14:39:10Z Photooxygenation of pregnanes Irradiation Mass spectrometry Nuclear magnetic resonance spectroscopy Olefins Reaction kinetics Alkene moieties Oxygenated products Photooxygenation Steroids Oxygen 3 [[(tert butyl)dimethylsilyl]oxy] 21 norpregn 17(20) ene 3 [[(tert butyl)dimethylsilyl]oxy] 21 norpregna 5,17(20) dien 16 ol 3 [[(tert butyl)dimethylsilyl]oxy] 5,17(20) dien 21 ol acetate 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) en 16 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) en 16 ol acetate 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) ene 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) dien 16 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) dien 21 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) diene alkene androstane derivative epiandrosterone ethylene oxide hydroperoxide oxygen prasterone pregnane derivative pyridine rose bengal steroid unclassified drug article carbon nuclear magnetic resonance chemical reaction irradiation mass spectrometry matrix assisted laser desorption ionization time of flight mass spectrometry oxygenation photooxidation priority journal proton nuclear magnetic resonance The course of the singlet-oxygen reaction with pregn-17(20)-enes and pregn-5,17(20)-dienes was studied to compare the reactivity of the two alkene moieties present in some steroid families. Thus, from commercially available (3β,5α)-hydroxy-androstan-17-one and (3β)-3-hydroxyandroxst-5- en-17-one, the following 3-{[(tertbutyl)dimethylsilyl]oxy}-substituted, 17(20)-unsaturated pregnanes were prepared (see Fig. 1): (3β,5α)-21- norpregn-17(20)-ene 1; (3β,5α,17Z)-pregn-17(20)-ene 2, (3β,5α,16α,17E)-pregn-17(20)-en-16-ol 3, (16β,5α, 17E-pregn-17(20)-en-16-ol 4, (3β,5α,16β,17E)-pregn-17(20)-en-16- ol acetate 5, (3β,16α)-21-norpregna-5,17(20)-dien-16-ol 6, (3β,16α,17E)-pregna-5,17(20)-dien-16-ol 7, (3β,17Z)-pregna-5, 17(20)-diene 8, (3β,17E)-pregna-5,17(20)-dien-21-ol 9 and (3β,17E)-5,17(20)-dien-21-ol acetate 10. The oxygenated products (see Fig. 2) obtained from 1-10 and 1O2, generated by irradiation of Rose Bengal in 3O2-saturated pyridine solution, were characterized by 1H-, 13C-NMR, and MS (EI, FAB, HR-EI, ESI- and UV-MALDI-TOF) data. Major products were those formed by the ene reaction involving as intermediates the corresponding hydroperoxides and the cyclic tautomers of the allylic hydroperoxides, i.e., the corresponding oxiranium oxide-like intermediate (Scheme 5). 2004 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_0018019X_v87_n12_p2987_Ponce http://hdl.handle.net/20.500.12110/paper_0018019X_v87_n12_p2987_Ponce |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Irradiation Mass spectrometry Nuclear magnetic resonance spectroscopy Olefins Reaction kinetics Alkene moieties Oxygenated products Photooxygenation Steroids Oxygen 3 [[(tert butyl)dimethylsilyl]oxy] 21 norpregn 17(20) ene 3 [[(tert butyl)dimethylsilyl]oxy] 21 norpregna 5,17(20) dien 16 ol 3 [[(tert butyl)dimethylsilyl]oxy] 5,17(20) dien 21 ol acetate 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) en 16 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) en 16 ol acetate 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) ene 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) dien 16 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) dien 21 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) diene alkene androstane derivative epiandrosterone ethylene oxide hydroperoxide oxygen prasterone pregnane derivative pyridine rose bengal steroid unclassified drug article carbon nuclear magnetic resonance chemical reaction irradiation mass spectrometry matrix assisted laser desorption ionization time of flight mass spectrometry oxygenation photooxidation priority journal proton nuclear magnetic resonance |
| spellingShingle |
Irradiation Mass spectrometry Nuclear magnetic resonance spectroscopy Olefins Reaction kinetics Alkene moieties Oxygenated products Photooxygenation Steroids Oxygen 3 [[(tert butyl)dimethylsilyl]oxy] 21 norpregn 17(20) ene 3 [[(tert butyl)dimethylsilyl]oxy] 21 norpregna 5,17(20) dien 16 ol 3 [[(tert butyl)dimethylsilyl]oxy] 5,17(20) dien 21 ol acetate 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) en 16 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) en 16 ol acetate 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) ene 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) dien 16 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) dien 21 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) diene alkene androstane derivative epiandrosterone ethylene oxide hydroperoxide oxygen prasterone pregnane derivative pyridine rose bengal steroid unclassified drug article carbon nuclear magnetic resonance chemical reaction irradiation mass spectrometry matrix assisted laser desorption ionization time of flight mass spectrometry oxygenation photooxidation priority journal proton nuclear magnetic resonance Photooxygenation of pregnanes |
| topic_facet |
Irradiation Mass spectrometry Nuclear magnetic resonance spectroscopy Olefins Reaction kinetics Alkene moieties Oxygenated products Photooxygenation Steroids Oxygen 3 [[(tert butyl)dimethylsilyl]oxy] 21 norpregn 17(20) ene 3 [[(tert butyl)dimethylsilyl]oxy] 21 norpregna 5,17(20) dien 16 ol 3 [[(tert butyl)dimethylsilyl]oxy] 5,17(20) dien 21 ol acetate 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) en 16 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) en 16 ol acetate 3 [[(tert butyl)dimethylsilyl]oxy]pregn 17(20) ene 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) dien 16 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) dien 21 ol 3 [[(tert butyl)dimethylsilyl]oxy]pregna 5,17(20) diene alkene androstane derivative epiandrosterone ethylene oxide hydroperoxide oxygen prasterone pregnane derivative pyridine rose bengal steroid unclassified drug article carbon nuclear magnetic resonance chemical reaction irradiation mass spectrometry matrix assisted laser desorption ionization time of flight mass spectrometry oxygenation photooxidation priority journal proton nuclear magnetic resonance |
| description |
The course of the singlet-oxygen reaction with pregn-17(20)-enes and pregn-5,17(20)-dienes was studied to compare the reactivity of the two alkene moieties present in some steroid families. Thus, from commercially available (3β,5α)-hydroxy-androstan-17-one and (3β)-3-hydroxyandroxst-5- en-17-one, the following 3-{[(tertbutyl)dimethylsilyl]oxy}-substituted, 17(20)-unsaturated pregnanes were prepared (see Fig. 1): (3β,5α)-21- norpregn-17(20)-ene 1; (3β,5α,17Z)-pregn-17(20)-ene 2, (3β,5α,16α,17E)-pregn-17(20)-en-16-ol 3, (16β,5α, 17E-pregn-17(20)-en-16-ol 4, (3β,5α,16β,17E)-pregn-17(20)-en-16- ol acetate 5, (3β,16α)-21-norpregna-5,17(20)-dien-16-ol 6, (3β,16α,17E)-pregna-5,17(20)-dien-16-ol 7, (3β,17Z)-pregna-5, 17(20)-diene 8, (3β,17E)-pregna-5,17(20)-dien-21-ol 9 and (3β,17E)-5,17(20)-dien-21-ol acetate 10. The oxygenated products (see Fig. 2) obtained from 1-10 and 1O2, generated by irradiation of Rose Bengal in 3O2-saturated pyridine solution, were characterized by 1H-, 13C-NMR, and MS (EI, FAB, HR-EI, ESI- and UV-MALDI-TOF) data. Major products were those formed by the ene reaction involving as intermediates the corresponding hydroperoxides and the cyclic tautomers of the allylic hydroperoxides, i.e., the corresponding oxiranium oxide-like intermediate (Scheme 5). |
| title |
Photooxygenation of pregnanes |
| title_short |
Photooxygenation of pregnanes |
| title_full |
Photooxygenation of pregnanes |
| title_fullStr |
Photooxygenation of pregnanes |
| title_full_unstemmed |
Photooxygenation of pregnanes |
| title_sort |
photooxygenation of pregnanes |
| publishDate |
2004 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_0018019X_v87_n12_p2987_Ponce http://hdl.handle.net/20.500.12110/paper_0018019X_v87_n12_p2987_Ponce |
| _version_ |
1768545769139208192 |