Stereoselective semisynthesis of uzarigenin and allo-uzarigenin

Herein, we report the concise semisynthesis of the natural cardenolide uzarigenin and its diastereoisomer allo-uzarigenin in nine and seven steps, respectively, starting from the broadly available epi-androsterone. For this purpose, the synthetic strategy for the stereoselective introduction of the...

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Bibliographic Details
Published in:Organic chemistry frontiers an international journal of organic chemistry 2023-03, Vol.10 (6), p.1435-1440
Main Authors: Sarah Al Muthafer, Schissler, Christoph, Koch, Vanessa, Kühner, Hannes, Nieger, Martin, Bräse, Stefan
Format: Article
Language:English
Subjects:
Carbon radioisotopes
Chemical reactions
Cross coupling
Hydrogenation
Organic chemistry
Oxidation
Semisynthesis
Stereoselectivity
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Summary:Herein, we report the concise semisynthesis of the natural cardenolide uzarigenin and its diastereoisomer allo-uzarigenin in nine and seven steps, respectively, starting from the broadly available epi-androsterone. For this purpose, the synthetic strategy for the stereoselective introduction of the β-hydroxy group at C-14 via Mukaiyama oxidation is discussed. Additionally, the installation of the butenolide ring at C-17 is performed using a Stille-cross-coupling reaction with subsequent stereoselective hydrogenation of the C-16/C-17 double bond to exclusively give allo-uzarigenin. By directing the hydrogenation via a protecting group strategy, the C-17β isomer can also be obtained stereoselectively.
ISSN:2052-4110
2052-4110
DOI:10.1039/d2qo01718k