Skip to Main content Skip to Navigation
Theses

Synthèse de 14B-hydroxyandrostanes et de systèmes (poly)hétérocycliques au départ d'oléfines activées reliées à des cycloalcanones et à des hétérocycles azotés

Abstract : In the first part of our work, we have developed highly diastereo/enantioselective Diels-Alder reactions to promote the synthesis of 14 beta-hydroxyandrostanes. Thus, numerous non-natural or natural racemic and optically pure 14 beta-hydroxyandrostanes were obtained. For example, starting from the 2-methyl-cyclopentane-1,3-dione, the synthesis of 14 beta-hydroxyandrostane derivatives bearing 5 to 7 stereogenic centers was readily achieved. Moreover, by using (R) or (S)-carvone as dienophile, the Diels-Alder reaction proved to be under a chemodivergent parallel kinetic resolution control leading to optically pure (ent)-14 beta-hydroxyandrostanes. The second part of our work was dealing with the synthesis of heterocyclic compounds like pyrrolizidinones, indolizidinones and 1,3-oxazines. For that purpose, we have shown that the latter were readily available by Lewis or Brønsted acids treatment of polyfunctionalized alpha-alkyloxyamides. Furthermore, by changing the nature of the Brønsted acid, pyrrolizidinones and indolizidinones derivatives were obtained allowing a formal synthesis of (+/-)-tashiromine. Finally, the synthesis of the tricyclic cores found in cedranoids and quadranes/subersonanes sesquiterpenes was achieved, the key step being a tri-n-butylphosphine promoted intramolecular Morita-Baylis-Hillman reaction.
Document type :
Theses
Complete list of metadatas

Cited literature [219 references]  Display  Hide  Download

https://tel.archives-ouvertes.fr/tel-02003528
Contributor : Abes Star :  Contact
Submitted on : Friday, February 1, 2019 - 12:14:12 PM
Last modification on : Wednesday, October 14, 2020 - 4:12:16 AM
Long-term archiving on: : Thursday, May 2, 2019 - 7:04:27 PM

File

PETER_Clovis_2017_ED222.pdf
Version validated by the jury (STAR)

Identifiers

  • HAL Id : tel-02003528, version 1

Collections

Citation

Clovis Peter. Synthèse de 14B-hydroxyandrostanes et de systèmes (poly)hétérocycliques au départ d'oléfines activées reliées à des cycloalcanones et à des hétérocycles azotés. Chimie organique. Université de Strasbourg, 2017. Français. ⟨NNT : 2017STRAF024⟩. ⟨tel-02003528⟩

Share

Metrics

Record views

74

Files downloads

67