Keywords: catalysis, synthetic methodology, biomass Internship Duration: 30/11/-1 - 30/11/-1
Head of the hosting team: Cantat Thibault
Website: Click here
Address of the host laboratory: LCMCE/NIMBE Team CEA Paris-Saclay/Paris Saclay university CEA Saclay, bât 125 91191 Gif-sur-Yvette Cedex France
Supervisor: Anthore-Dalion LucileE-mail: lucile.anthore@cea.fr Phone: +3369089159
The easy access to energy and carbon-based raw materials offered by fossil feedstock allowed the rapid growth of our society. Nevertheless, the expected depletion of fossil resources and climate change require changing for a more sustainable model. Bio-based feedstock is a promising carbon source to substitute petrochemicals but requires a drastic change in the actual model. While the current paradigm relies on producing energy and high-value molecules through oxidation steps, a model based on the 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 and deoxygenation. Esters (RCO2R’) are abundant and readily available materials but suffer from a limited amount of transformation (reduction, deoxygenation, transesterification). They can yet be seen as a source of both a nucleophile R and an electrophile R’ upon decarboxylative coupling, with CO2 acting as a traceless linker. Such reactivity is today constrained to carboxylic acids and activated esters.1 The decarboxylative recombination of esters relies on two main challenges: the C–O sigma bond activation and the decarboxylation of the carboxylate moiety. This master project will focus on the metal-catalyzed decarboxylative cross-coupling of aryl benzoates to obtain biaryl derivatives (R, R’=aromatic). The internship project will draw on ongoing research in our laboratory on the reactivity of esters and decarboxylation reactions.2
The student will develop his/her skills in organic and organometallic synthesis, working under an inert atmosphere (Schlenk lines, gloveboxes), as well as in the analysis of chemical compounds (NMR, GC, HPLC-MS, IR, X-Ray). The intern will also be trained in experimental mechanistic investigations and DFT computations.
1 S. Muraka, Adv. Synth. Catal. 2018, 320, 1735; R. Shang, L. Liu, Sci. China Chem. 2011, 54, 1670. 2 E. Crochet, L. Anthore-Dalion, T. Cantat Angew. Chem. Int. Ed. 2023, 62, e202214069; T. Cantat, D. Audisio, et al. J. Am. Chem. Soc. 2019, 780.
