Missions

Multi-catalytic decarboxylative cross-coupling of esters
Transition-metal catalyzed cross-coupling reactions have transformed carbon-carbon bond formation in complex organic molecules, revolutionizing fields like pharmaceutical and agrochemical industries, polymers, and natural product synthesis. Despite their vast applications, these reactions heavily rely on toxic organic halides and organometallic reagents that require multiple preparation steps and often lack stability. Carboxylic esters (RCOOE) offer a promising alternative as they are readily available, potentially bio-sourced, and can serve as bifunctional partners in cross-coupling reactions. The ester's R and E groups can indeed act as nucleophiles and electrophiles upon carbon dioxide extrusion, forming carbon-carbon bonds (R–E) by recombination in an exergonic transformation. However, unlocking the full potential of esters faces a significant kinetic challenge due to the difficult activation of strong C–O bonds. This challenge has limited applications to reactive substrates like allyl esters (E = allyl).
In the frame of the ERC starting grant DECAF, the post-doctoral researcher will unlock the decarboxylative recombination of alkyl esters by developing a new multi-catalytic approach under photoirradiation, using a combination of non-noble metals (Fe, Ce, Ni…). The project will draw on ongoing research in our laboratory on the reactivity of esters, C–O bond activations, and preliminary unpublished results. All along the project, a strong focus will be made on the understanding of the mechanistic at play via experimental and/or computational investigations. The researcher 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.

Activités

- Developing and studying the homogeneous multicatalytic system for the decarboxylative recombination of esters
- Study of the reaction scope
- Mechanistic studies

Compétences

The applicant must hold a PhD in molecular chemistry (organic chemistry or organometallic chemistry). Experience in catalysis and mechanistic studies will be appreciated.

Contexte de travail

The research 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/