Skip to Main content Skip to Navigation
Theses

TIPS-Diazoacétone : nouveau synthon pour l’élaboration de chaînes diazocarbonylées C-silylées – Application à la synthèse d’oxacycles silylés à 5 chaînons

Abstract : Α-diazocarbonyl compounds are important synthetic intermediates in organic chemistry. Decomposition of the diazo functionality promotes a wide range of synthetic transformations (X-H insertions, migrations or rearrangements). Few synthetic pathways are available to access these highly valuable α-diazocarbonyl scaffolds. In this context, our objective was to study the synthetic potential of the three-carbon building-block TIPS-diazoacetone to elaborate a range of original C-silyl diazocarbonylated compounds, through methyl-side aldol addition. More than a protective group for the diazo carbon, the TIPS moiety is a structural element allowing the access to original silylated molecules via diazo decomposition. The first part of this work was devoted to the development of a safe method to access diazoacetone, the direct precursor of TIPS-diazoacetone, without handling potentially explosive organic azides. A convenient one-pot, three-step procedure was implemented, involving in-situ formation of the intermediate organic azide. Transposition of the method to continuous flow process was also studied. The methyl-side aldolisation of TIPS-diazoacetone was then explored. Several parameters were investigated, providing conditions which allowed the synthesis of the expected original C-silylated aldols in good yields and in a reproducible way. Transformation of our C-silylated diazoaldols into original silylated compounds, through diazo decomposition, was initiated in the third part of the project. Intramolecular O-H insertion and Wolff rearrangement could be be achieved under acid catalysis to provide original C- or O-silylated five-membered O-heterocycles.
Document type :
Theses
Complete list of metadatas

Cited literature [132 references]  Display  Hide  Download

https://tel.archives-ouvertes.fr/tel-02900288
Contributor : Abes Star :  Contact
Submitted on : Thursday, July 16, 2020 - 1:03:35 AM
Last modification on : Thursday, July 16, 2020 - 3:44:16 AM

File

2019LEMA1034.pdf
Version validated by the jury (STAR)

Identifiers

  • HAL Id : tel-02900288, version 1

Citation

Sigrid Gavelle. TIPS-Diazoacétone : nouveau synthon pour l’élaboration de chaînes diazocarbonylées C-silylées – Application à la synthèse d’oxacycles silylés à 5 chaînons. Chimie organique. Université du Maine, 2019. Français. ⟨NNT : 2019LEMA1034⟩. ⟨tel-02900288⟩

Share

Metrics

Record views

64

Files downloads

65