Mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones
Utilization of 17-keto-androstanes as starting materials for the synthesis of α- or β-oriented steroidal 20→16-γ-carbolactones has been explored following two different strategies. A highly efficient, stereospecific protocol has been developed for the β-oriented cis-γ-lactone. A different approach,...
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todo:paper_09680896_v7_n5_p943_Bruttomesso2023-10-03T15:55:19Z Mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones Bruttomesso, A.C. Doller, D. Gros, E.G. Biosynthesis Natural products NMR Stereospecificity Steroids and sterols carbonyl derivative hydroxyl group ketol lactone derivative steroid tomatine article carbon nuclear magnetic resonance reaction analysis synthesis Androstanols Lactones Magnetic Resonance Spectroscopy Models, Chemical Models, Molecular Spironolactone Utilization of 17-keto-androstanes as starting materials for the synthesis of α- or β-oriented steroidal 20→16-γ-carbolactones has been explored following two different strategies. A highly efficient, stereospecific protocol has been developed for the β-oriented cis-γ-lactone. A different approach, involving prior attachment of a 3-carbon side chain on C-17 of a 17-oxo-16β-acetoxy-androstane led to the epimeric, α-oriented lactone. The mechanism of the rearrangement of epimeric 16β- or 16α-hydroxy-17-keto-androstanes to 17β-hydroxy-16-keto-androstanes was studied by 13C NMR spectroscopy. The former occurs through a 1,2-sigmatropic H-shift, while the latter is likely to take place by simple enolization-reprotonation. Copyright (C) 1999 Elsevier Science Ltd. Fil:Bruttomesso, A.C. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Doller, D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Gros, E.G. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_09680896_v7_n5_p943_Bruttomesso |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Biosynthesis Natural products NMR Stereospecificity Steroids and sterols carbonyl derivative hydroxyl group ketol lactone derivative steroid tomatine article carbon nuclear magnetic resonance reaction analysis synthesis Androstanols Lactones Magnetic Resonance Spectroscopy Models, Chemical Models, Molecular Spironolactone |
| spellingShingle |
Biosynthesis Natural products NMR Stereospecificity Steroids and sterols carbonyl derivative hydroxyl group ketol lactone derivative steroid tomatine article carbon nuclear magnetic resonance reaction analysis synthesis Androstanols Lactones Magnetic Resonance Spectroscopy Models, Chemical Models, Molecular Spironolactone Bruttomesso, A.C. Doller, D. Gros, E.G. Mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones |
| topic_facet |
Biosynthesis Natural products NMR Stereospecificity Steroids and sterols carbonyl derivative hydroxyl group ketol lactone derivative steroid tomatine article carbon nuclear magnetic resonance reaction analysis synthesis Androstanols Lactones Magnetic Resonance Spectroscopy Models, Chemical Models, Molecular Spironolactone |
| description |
Utilization of 17-keto-androstanes as starting materials for the synthesis of α- or β-oriented steroidal 20→16-γ-carbolactones has been explored following two different strategies. A highly efficient, stereospecific protocol has been developed for the β-oriented cis-γ-lactone. A different approach, involving prior attachment of a 3-carbon side chain on C-17 of a 17-oxo-16β-acetoxy-androstane led to the epimeric, α-oriented lactone. The mechanism of the rearrangement of epimeric 16β- or 16α-hydroxy-17-keto-androstanes to 17β-hydroxy-16-keto-androstanes was studied by 13C NMR spectroscopy. The former occurs through a 1,2-sigmatropic H-shift, while the latter is likely to take place by simple enolization-reprotonation. Copyright (C) 1999 Elsevier Science Ltd. |
| format |
JOUR |
| author |
Bruttomesso, A.C. Doller, D. Gros, E.G. |
| author_facet |
Bruttomesso, A.C. Doller, D. Gros, E.G. |
| author_sort |
Bruttomesso, A.C. |
| title |
Mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones |
| title_short |
Mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones |
| title_full |
Mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones |
| title_fullStr |
Mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones |
| title_full_unstemmed |
Mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones |
| title_sort |
mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones |
| url |
http://hdl.handle.net/20.500.12110/paper_09680896_v7_n5_p943_Bruttomesso |
| work_keys_str_mv |
AT bruttomessoac mechanisticstudiesoftherearrangementsofsteroidal1617ketolsandsynthesesof2016cisgcarbolactones AT dollerd mechanisticstudiesoftherearrangementsofsteroidal1617ketolsandsynthesesof2016cisgcarbolactones AT groseg mechanisticstudiesoftherearrangementsofsteroidal1617ketolsandsynthesesof2016cisgcarbolactones |
| _version_ |
1807318126185938944 |