Description du sujet de thèse

The objective of the thesis is to develop catalytic enantioselective and stereoconvergent isomerizations of (E)/(Z) vinyl boronic ester mixtures. However, most examples of enantioselective isomerization of olefins requires the use of the pure (E) or (Z) isomer. Our catalytic system would enable isomer mixtures to converge to a single enantiopure compound, therefore designing sustainable synthetic sequences of high-value chemicals. The targeted chiral allylic boronic esters are molecules of interest, as they can be easily transformed by a wide range of functionalization finding applications in fine chemical synthesis. A strategy based on dual iron/photoredox catalysis will be developed. To achieve this goal, tailored chiral iron-imido catalysts will be designed. An approach combining organometallic synthesis of imido iron complexes and mechanism investigations leading to application in enantioselective catalysis will be implemented. Characterization techniques such as NMR, Mössbauer, UV-Vis spectroscopies, chromatography (GC, HPLC), X-ray diffraction, fluorometry and cyclic voltammetry will be used. The outcome of this study will provide a light-promoted sustainable access to high-value enantiopure molecules from isomeric mixtures, and advance the field of iron catalysis, an abundant and non-toxic transition metal.
The candidate will be involved into the following tasks:
- Synthesis of sensitive organometallic iron catalysts (inert atmosphere, glovebox technique);
- Mechanism investigations (stoichiometric studies, isolation of key intermediates, ground-state photophysic studies, kinetic studies);
- Optimization of enantioselective dual iron/photoredox catalysis and scope investigation.

Contexte de travail

This PhD position will be conducted in two well-established institutes:
 First period of 18 months in France – Rennes Chemical Sciences Institute, UMR 6226 – team Organometallics: Materials and Catalysis (OMC) with Dr. Coralie Duchemin and Prof. Christophe Darcel (funding ARED program, region Bretagne).
 Second period of 18 months in Germany – Leibniz Institute for Catalysis (LIKAT Rostock) in the group of Prof. Matthias Beller.

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

The candidate should be familiar with laboratory good practices associated with chemical hazards.

Informations complémentaires

The candidate will hold a M2 degree or equivalent in molecular chemistry. A previous experience in organic synthesis, homogenous (photo)catalysis or/and in organometallic synthesis is required to apply. Previous experience with Schlenk techniques and gloveboxes will be appreciated. Enthusiasm, autonomy, scientific curiosity and ability to communicate in English are required qualities.
Applications should contain (i) a cover letter, (ii) an updated CV, (iii) a full list of transcripts for higher education (Licence/BsC and Master), (iv) a list of 1 to 3 persons that can be contacted for recommendation.