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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Autores principales: Bruttomesso, Andrea Claudia, Doller, Darío, Gros, Eduardo Gervasio
Publicado: 1999
Materias:
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
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09680896_v7_n5_p943_Bruttomesso
http://hdl.handle.net/20.500.12110/paper_09680896_v7_n5_p943_Bruttomesso
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_09680896_v7_n5_p943_Bruttomesso
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spelling paper:paper_09680896_v7_n5_p943_Bruttomesso2025-07-30T18:35:03Z Mechanistic studies of the rearrangements of steroidal 16,17-ketols and syntheses of 20→16-cis-γ-carbolactones Bruttomesso, Andrea Claudia Doller, Darío Gros, Eduardo Gervasio 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. 1999 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09680896_v7_n5_p943_Bruttomesso 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, Andrea Claudia
Doller, Darío
Gros, Eduardo Gervasio
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.
author Bruttomesso, Andrea Claudia
Doller, Darío
Gros, Eduardo Gervasio
author_facet Bruttomesso, Andrea Claudia
Doller, Darío
Gros, Eduardo Gervasio
author_sort Bruttomesso, Andrea Claudia
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
publishDate 1999
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09680896_v7_n5_p943_Bruttomesso
http://hdl.handle.net/20.500.12110/paper_09680896_v7_n5_p943_Bruttomesso
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AT groseduardogervasio mechanisticstudiesoftherearrangementsofsteroidal1617ketolsandsynthesesof2016cisgcarbolactones
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