Description du sujet de thèse

General context : The urethane (or carbamate) functional group is a key chemical motif in both the pharmaceutical industry and materials science. It is found in many drugs as well as in polyurethanes (PUs), high-tonnage polymers, which rank among the top six in terms of annual production. These materials have a wide range of applications, including foams, coatings, adhesives, insulation, and biomedical devices. However, the industrial synthesis of urethane-containing molecules and macromolecules still relies on isocyanates, highly toxic and hazardous compounds. Therefore, the search for more eco-friendly synthetic pathways is essential for producing both pharmaceuticals and PUs with a reduced environmental impact.
Project : The overall aim of this project is to develop an efficient synthetic methodology for preparing urethanes through dehydrogenative couplings (DCs) of alcohols and N-substituted formamides (R1OH + R2R3N-C(O)H = urethane). Currently reported catalysts show moderate activities and/or selectivities.3 This project aims to develop highly efficient catalysts based on earth-abundant metals—particularly copper—to drive these DC with excellent yields, eliminating the need for formamide as a solvent. Preliminary results obtained in the laboratory suggest that tuning the copper coordination sphere is a key lever to achieving the project's goals. The optimized catalytic systems will be applied at two levels: i) Molecular level: by preparing a pharmaceutical intermediate1 ; ii) Macromolecular level: by applying the DC to difunctional substrates (biosourced diol and diformamide) to prepare and characterize PUs. This novel approach holds significant potential to enable the production of drugs and PUs with a reduced environmental impact, as conventional isocyanates are replaced by N-substituted formamides derived from CO2, an inexpensive and highly accessible reagent. The PhD's tasks will therefore be to:
• design, prepare and characterize organic ligands capable of modulating the electronic and steric properties of copper, as well as the corresponding complexes.
• evaluate the catalytic properties of the Cu complexes prepared in model molecular couplings.
• illustrate the potential of optimized catalysts in the preparation of a pharmaceutical intermediate & of PUs.
• study the mechanisms experimentally (for ex. characterization and/or isolation of catalytic intermediates).
Desired profile: Applicants should have a solid background in molecular chemistry. Prior experience in catalysis and/or coordination chemistry is highly desirable. Due to the multidisciplinary scope of the project, candidates are expected to demonstrate adaptability, scientific curiosity, autonomy, and a rigorous approach to research. Good oral and written communication skills, along with the ability to work collaboratively, are also important.

Contexte de travail

The Charles Gerhardt Institute Montpellier (UMR 5253) is a multidisciplinary research laboratory comprised of five departments and nearly 500 staff members. The ICGM contributes to the development of chemistry research with the aim of developing and characterizing complex materials with functionalities that have a high societal impact, particularly in the fields of health, the environment, and energy.

The ICGM's expertise in the entire skill chain for the development of complex materials favorably positions its research activities not only within the Montpellier region but also nationally and internationally.

The "Materials Chemistry for Humanity and Society" project, led by the entire UMR, is structured around five complementary areas:

Molecular Materials
Macromolecular Materials
Porous and Hybrid Materials
Materials for Energy
Theoretical Physical Chemistry

These five areas, which interact closely with each other, allow research to be organized around the different time and space scales that must be mastered to successfully design innovative complex functional materials for applications in the fields of health, the environment, and energy.

One of the keystones of all this research is the desire to understand and utilize the different types of intermolecular interactions to propose synthesis strategies that highlight cooperative processes and synergies between different functional units.

Le poste se situe dans un secteur relevant de la protection du potentiel scientifique et technique (PPST), et nécessite donc, conformément à la réglementation, que votre arrivée soit autorisée par l'autorité compétente du MESR.

Contraintes et risques

n.a.