Hemisynthesis of 2,3,4-(13)C3-1,4-Androstadien-3,17-dione: A Key Precursor for the Synthesis of (13)C3-Androstanes and (13)C3-Estranes - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Organic Chemistry Année : 2018

Hemisynthesis of 2,3,4-(13)C3-1,4-Androstadien-3,17-dione: A Key Precursor for the Synthesis of (13)C3-Androstanes and (13)C3-Estranes

Résumé

In this contribution, we describe two simple and efficient routes for the preparation of keto-aldehyde 1, a key intermediate for the synthesis of (13)C3-androstanes and (13)C3-estranes. In the first route, the targeted aldehyde 1 was obtained in 40% overall yield from 1,4-androstadien-3,17-dione (3 mmol scale) via a two-step sequence involving a one-pot, abnormal ozonolysis/sulfur oxidation/retro-Michael/ozonolysis process. Alternatively, a second route from 4-androsten-3,17-dione, using a six-step sequence, was optimized to produce 40 mmol batches of the key intermediate 1 in 42% overall yield. At the final stage, the A-ring was reconstructed through a Wittig reaction with the 1-triphenylphosphoranylidene-(13)C3-2-propanone 2, followed by an intramolecular condensation assisted by thioacetic acid via a Michael addition/retro-Michael reaction sequence to provide 2,3,4-(13)C3-1,4-androstadien-3,17-dione.

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Chimie
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Dates et versions

hal-02140998 , version 1 (27-05-2019)

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Clément Berthonneau, Pierrick Nun, Matthieu Riviere, Mickael Pauvert, Fabrice Denes, et al.. Hemisynthesis of 2,3,4-(13)C3-1,4-Androstadien-3,17-dione: A Key Precursor for the Synthesis of (13)C3-Androstanes and (13)C3-Estranes. Journal of Organic Chemistry, 2018, 83 (7), pp.3727-3737. ⟨10.1021/acs.joc.7b03216⟩. ⟨hal-02140998⟩
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