Description du sujet de thèse

The easy access to energy and carbon-based raw materials provided by fossil feedstocks allowed for the rapid growth of our society. Nevertheless, the expected depletion of fossil resources and climate change require a switch to a more sustainable model. Bio-based feedstock is a promising carbon source to substitute petrochemicals, but requires a drastic shift from the current model. While the current paradigm relies on the production of energy and high-value molecules through oxidation steps, a model based on Carbon Circular Economy, i.e., the transformation of CO2 and biomass feedstock that are already highly oxidized materials, demands the development of new methodologies for reduction, deoxygenation, and the direct use of oxygenated bonds to access functionalized and useful organic molecules.
In organic chemistry, cross-coupling reactions (Suzuki, Heck, Hiyama…) are one of the major tools for creating C–C bonds. However, they are still based mainly on the use of organic halides as electrophiles. In this project, the PhD candidate will demonstrate that readily available and abundant alkyl esters can serve as electrophilic coupling partners in cross-coupling reactions with alkenes. Esters can indeed be directly biosourced or easily synthesized from alkyl carboxylic acids and alcohols, thereby reducing the environmental impact of carbon-carbon bond formation.
The main objective of the project will be the development of catalytic Heck-type cross-coupling reactions, under both thermal and photo-activation, catalyzed by non-noble metals (Fe, Co…). To activate alkyl esters, we envisage the use of tandem catalysis, where two catalysts will work in synergy to perform the reaction. The PhD project will draw on ongoing research in our laboratory on the reactivity of esters, C–O bond activations, and preliminary unpublished results.
The PhD candidate will develop his/her skills in catalysis, organic and organometallic synthesis, working under inert atmosphere (Schlenk lines, gloveboxes), as well as in the analysis of chemical compounds (NMR, GC-MS, IR, X-Ray). The student will also have access to modern optimization methods for catalytic systems, such as highthrouput experimentation (HTE, collaboration with the HTE platform of the CEA Saclay) and DFT computations, and be trained in these techniques if he/she so wishes.


Relevant references :
[1] E. Crochet, L. Anthore-Dalion, T. Cantat Angew. Chem. Int. Ed. 2023, 62, e202214069.
[2] N. De Riggi, A. Imberdis, E. Nicolas, T. Cantat Organometallics 2024, 43, 2466.

Contexte de travail

The thesis will be carried out at the Laboratory of Molecular Chemistry and Catalysis for Energy (LCMCE), a research group within the NIMBE unit located at CEA Saclay (France), in immediate proximity to the Université Paris-Saclay campus. The group comprises an average of twenty members, including eight permanent researchers. The PhD student will be supervised by Lucile Anthore-Dalion, a researcher specializing in synthetic methodology.
The project will build upon the laboratory's expertise in C–O bond activation, decarboxylation, and photoredox catalysis. The LCMCE brings together a team of molecular chemists with specialized skills in organic, organometallic, computational chemistry, and catalysis, all driven by a passion for creating and breaking bonds using organic and organometallic catalysts.
Our research focuses on converting oxygenated molecules (C1 molecules, plastic waste, biomass byproducts, nitrogen oxides, etc.) into valuable chemicals and developing renewable hydrides, with the goal of closing the carbon and nitrogen cycles and promoting a circular economy. Through a rational, mechanism-based approach, we design novel transformations in homogeneous catalysis (organic and organometallic).
The LCMCE is fully equipped to support the proposed project. For synthesis, gloveboxes under argon atmosphere, Schlenk lines, and autoclaves capable of reaching pressures up to 180 bar and temperatures up to 250 °C are available. Our facilities also include: two photoreactors with lamps of varying intensity and spectra (6 W white LEDs, Kessil lamps at 390 nm, 440 nm, and 467 nm at 45 W), a 400 MHz multi-nuclear NMR spectrometer, an X-ray diffractometer, a GC for common gas analysis, a GC/MS, and an HPLC/MS. DFT calculations will be performed using annual allocations on national high-performance computing centers.
More details here: https://iramis.cea.fr/en/nimbe/lcmce/

Contraintes et risques

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