Palladium catalyzed functionalization of nonactivated C(sp3)-H bonds
type: Distribution
access URL: https://theses.hal.science/tel-00704011
format: HTML
issued: 2026-05-16T04:59:21.111851
modified: 2026-05-16T04:59:21.039657

test_moissonnage_selune
type: Agent

Palladium catalyzed functionalization of nonactivated C(sp3)-H bonds
type: Dataset
contact point: Organization
  fn: CCSD
keyword: activation-c-h
keyword: catalyse-organometallique
keyword: c-c-bond-formation
keyword: organometallic-catalysis
keyword: formation-de-liaisons-c-c
keyword: cyclobutenes
keyword: enolate
keyword: cyclobutanes
keyword: palladium
keyword: ester
keyword: c-h-functionalization
keyword: -arylation
keyword: infoeu-reposemanticsdoctoralthesis
keyword: -h-elimination
keyword: theses
keyword: fonctionnalisation-c-h
keyword: chimothechemical-sciencesother
keyword: c-h-activation
landing page: https://theses.hal.science/tel-00704011
description: The direct functionalization of C-H bonds represents an atom- and step-economical alternative to more traditional synthetic methods based on functional group transformation, which often require multi-step sequences. In particular, transition-metal catalysis has recently emerged as a powerful tool to functionalize otherwise unreactive C-H bonds. In this context, we first investigated the extension of a methodology that has been developed in our laboratory for the synthesis of benzocyclobutenes via C(sp3)-H activation, to non aromatic compounds. Substrates have been synthesized in order to be evaluated in the reaction to form cyclobutenes or cyclobutanes. The process was not selective and several by-products were formed via pericylic reactions or rearrangements of the intermediate palladacycle. Our research has also focused on a conceptually new palladium catalyzed β-C-H arylation of carboxylic esters method. The investigations consisted of a complete optimization of the reaction conditions, an evaluation of the scope and elucidation of the mechanism. It was found that this type of [bêta]-arylation is mechanistically related to α-arylation because it involves the formation of a palladium-enolate. Computational studies (DFT calculations, C. Kefalidis et E. Clot) confirmed the proposed mechanism. Our strategy allowed a mild and efficient intermolecular arylation reaction from aryl halides bearing an ortho electronegative group, giving rise to a range of synthetically useful functionalized carboxylic esters such as phenylalanine analogues and new fluorinated building blocks.
identifier: NNT: 2010LYO10175
issued: 2026-05-16T04:59:21.077342
language: fr
modified: 2026-05-16T04:59:21.077348