Dylan BOUETARD PhD defense
Alkylations et allylations asymétriques catalysées par des complexes de cuivre chiraux
Freitag 7 März 2025, 10:00Passed
Organometallics: Materials & Catalysis (OMC) team
Abstract
Asymmetric alkylation and allylation catalyzed by chiral copper complexes are key organic reactions for the selective and controlled formation of carbon-carbon bonds. Thus, asymmetric allylic alkylation (AAA) with copper has been extensively employed in the total synthesis of natural and bioactive molecules. Asymmetric allyl-allyl coupling and asymmetric conjugate allylation, in turn, represent emerging methodologies for the formation of complex molecular building blocks. The success of these transformations relies on the development of effective chiral ligands.
Therefore, this doctoral research initially focused on the development of a new class of N-heterocyclic carbenes (NHCs): N- hydroxyalkyl pyrid-2-ylidene.
The evaluation of these ligands in AAA led to the formation of chiral 1,4-diene products with enantioselectivities of up to 93%. The developed methodology was then applied in the formal synthesis of Phorbasine C. The development of a method for allyl transfer via retro-allylation with copper was subsequently carried out using high-throughput experimentation (HTE). A library of 24 chiral ligands (phosphines, NHCs, CAACs) was screened. Promising enantioselectivities (up to 76% ee) were observed for the asymmetric methylation of carbonyls, and preliminary results were obtained in conjugate allylation.
Jury
Pr. Véronique Michelet (Université de Nice) - Reporter
Dr. Olivier Baslé (LCC Toulouse) - Reporter
Dr. Florian Medina (J&J Beerse) - Examiner
Dr. Sophie Guillaume (ISCR, Université de Rennes) - Examiner
Dr. Eugénie Romero-Laboureur (CEA Saclay) - invited
Dr. Marc Mauduit (ISCR, Université de Rennes) - PhD supervisor
Contact
Marc Mauduit - marc.mauduit@ensc-rennes.fr
