Artículo
Ponce, M.A.; Erra-Balsells, R.; Bruttomesso, A.C.; Gros, E.G. "Photooxygenation of pregnanes" (2004) Helvetica Chimica Acta. 87(12):2987-3003
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Abstract:
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).
Registro:
| Documento: | Artículo |
| Título: | Photooxygenation of pregnanes |
| Autor: | Ponce, M.A.; Erra-Balsells, R.; Bruttomesso, A.C.; Gros, E.G. |
| Filiación: | CIHIDECAR-CONICET, Departamento de Quimica Organica, Universidad de Buenos Aires, 1428-Buenos Aires, Argentina UMYMFOR-CONICET, Departamento de Quimica Organica, Universidad de Buenos Aires, 1428-Buenos Aires, Argentina |
| Palabras clave: | 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 |
| Año: | 2004 |
| Volumen: | 87 |
| Número: | 12 |
| Página de inicio: | 2987 |
| Página de fin: | 3003 |
| DOI: | http://dx.doi.org/10.1002/hlca.200490270 |
| Título revista: | Helvetica Chimica Acta |
| Título revista abreviado: | Helv. Chim. Acta |
| ISSN: | 0018019X |
| CODEN: | HCACA |
| CAS: | epiandrosterone, 481-29-8; ethylene oxide, 16002-48-5, 32587-16-9, 36376-18-8, 75-21-8; oxygen, 7782-44-7; prasterone, 53-43-0; pyridine, 110-86-1; rose bengal, 11121-48-5, 11139-83-6, 632-68-8 |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_0018019X_v87_n12_p2987_Ponce |
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Citas:
---------- APA ----------
Ponce, M.A., Erra-Balsells, R., Bruttomesso, A.C. & Gros, E.G. (2004) . Photooxygenation of pregnanes. Helvetica Chimica Acta, 87(12), 2987-3003.http://dx.doi.org/10.1002/hlca.200490270
---------- CHICAGO ----------
Ponce, M.A., Erra-Balsells, R., Bruttomesso, A.C., Gros, E.G. "Photooxygenation of pregnanes" . Helvetica Chimica Acta 87, no. 12 (2004) : 2987-3003.http://dx.doi.org/10.1002/hlca.200490270
---------- MLA ----------
Ponce, M.A., Erra-Balsells, R., Bruttomesso, A.C., Gros, E.G. "Photooxygenation of pregnanes" . Helvetica Chimica Acta, vol. 87, no. 12, 2004, pp. 2987-3003.http://dx.doi.org/10.1002/hlca.200490270
---------- VANCOUVER ----------
Ponce, M.A., Erra-Balsells, R., Bruttomesso, A.C., Gros, E.G. Photooxygenation of pregnanes. Helv. Chim. Acta. 2004;87(12):2987-3003.http://dx.doi.org/10.1002/hlca.200490270
