Selective and sustainable functionalization of cyclic imides and oxindoles under homogeneous catalysis
Organometallics: Materials & Catalysis (OMC) team
Abstract
'This PhD thesis presents the development of selective and sustainable methodologies for the C–H functionalization of cyclic imides and 3-oxindoles under homogeneous iridium catalysis. Building on the principles of transition-metal catalysis and ligand design, the work introduces simple, air-stable, and tunable click-derived and pyridine ligands that enable highly site- and regio-selective transformations on complex heterocyclic scaffolds that are biologically and pharmaceutically-relevant.
Mechanistic and structural studies revealed an unprecedented ligand deprotonation pathway mediated by B₂pin₂ for the case of the click ligands, providing new insights into ligand behavior under catalytic conditions. These ligands promote efficient proximal or distal C–H borylations of phthalimides and carbonyl-containing substrates under green and scalable conditions, while the use of pyridine ligands affords high turnover numbers with minimal waste. Extending this concept, triazolylquinoline proligands enabled the first fully selective C–H borylation of 3-oxindoles proximal to the carbonyl group, affording versatile boronic esters for further functionalization. The resulting derivatives exhibited tunable photophysical properties, highlighting their potential for photoemissive and photocatalytic applications. Finally, the thesis reports the racemic and enantioselective synthesis of 2,2-disubstituted 3-oxindoles via ligand modification, granting access to all four possible stereoisomers. Altogether, this work establishes new, practical paradigms in C–H activation chemistry by demonstrating that simple ligand architectures can rival sophisticated systems, paving the way toward rational, economical, and environmentally responsible catalytic processes with relevance to organic synthesis, materials science, and sustainability.'
Jury
Lucie NOREL, professeure des universités, Université de Rennes
Julie OBLE, professeure des universités, Sorbonne Université
Philippe DAUBAN, directeur des recherches, Institut de Chimie des Substances Naturelles
Tatiana BESSET, directrice des recherches, Université de Rouen
Clément MAZET, professeur des universités, Université de Genève
Sylvie DERIEN, maîtresse de conférences, Université de Rennes / PhD Co-Director
Mathieu ACHARD, maître de conférences, Université de Rennes / PhD Director
Rafael GRAMAGE-DORIA, chargé de recherche, Université de Rennes, / PhD Director
Contacts
Sylvie Derien, sylvie.derien@univ-rennes.fr
Mathieu Achard, mathieu.achard@univ-rennes.fr
Rafael Gramage-Doria, rafael.gramage-doria@univ-rennes.fr
