Description du sujet de thèse

[2.2]Paracyclophanes (pCps) are fascinating molecules with an unusual three-dimensional structure and intriguing physicochemical properties.[1] These compounds have been extensively used in material science as building blocks for through-space conjugated polymers and optoelectronic devices.[2] Owing to their planar chirality, pCps have also found numerous applications as ligands in asymmetric catalysis.[3] However, their use as organocatalysts remains relatively limited.[4] The development of novel processes promoted by these compounds would represent a significant advancement in cyclophane chemistry.
Photocatalysis is a fascinating field of research that harnesses light as an energy source to drive organic transformations. Over the years, various catalysts - both fully organic compounds and metal-based complexes - have been developed to reinvent known reactions or enable previously inaccessible ones.[5] However, controlling chirality in light-induced transformations remains a significant challenge.
In our laboratory, pCp derivatives have been successfully utilized as organophotocatalysts to promote different reactions under light irradiation.[6] In a recent collaboration with Dr. Thomas Boddaert (Université Paris-Saclay), we demonstrated that chirality control in the thio-Paternò–Büchi reaction[7] can potentially be achieved using our planar chiral photocatalysts.[8] The aim of this PhD thesis is to develop new, more efficient pCp-based photocatalysts by functionalizing their aromatic rings with various groups. This approach will build on our promising preliminary results to achieve more effective asymmetric thia-Paternò–Büchi reactions. A potential extension of this work also involves the development of circularly polarized light emitters, thereby opening the way to applications in other research fields
References: (1) Brown, C. J.; Farthing, A. C. Nature 1949, 164, 915. (2) Hassan, Z.; Lahann, J.; Bräse, S. Adv. Funct. Mater. 2024, 2410027. (3) Gibson, S. E.; Knight, J. D. Org. Biomol. Chem. 2003, 1, 1256. (4) Felder, S.; Wu, S.; Brom, J.; Micouin, L.; Benedetti, E. Chirality 2021, 33, 506. (5) Shaw, M. H.; Twilton, J.; MacMillan, D. W. C. J. Org. Chem. 2016, 81, 16, 6898. (6) Brom, J.; Maruani, A.; Turcaud, S.; Lajnef, S.; Peyrot, F.; Micouin, L.; Benedetti, E. Org. Biomol. Chem. 2024, 22, 59. (7) Lapuh, M. I.; Cormier, G.; Chergui, S.; Aitken, D. J.; Boddaert, T. Org. Lett. 2022, 24, 8375. (8) Unpublished preliminary results.

Contexte de travail

This position is part of a project funded by the French National Research Agency (ANR), involving a collaboration between two chemistry laboratories: the Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques (LCPBT, UMR 8601, Paris Cité University) and the Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO, UMR CNRS 8182, Paris-Saclay University).
The PhD candidate will primarily carry out their research at the Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques (UMR 8601, CNRS, Université Paris Cité, Paris 6th arrondissement), within the host team "New Synthetic Methods for the Chemistry–Biology Interface." The team's research encompasses a broad spectrum of topics in synthetic organic chemistry and chemical biology, with a particular emphasis on molecular innovation.

Contraintes et risques

The position involves exposure to chemical hazards, with risk management carried out in accordance with the applicable national regulations and the laboratory's internal safety rules.