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Sustainable biphasic organocatalysis into well-defined water-soluble core-shell nanoreactors



Lab: LCC

Duration: 6 months full-time internship

Latest starting date: 01/02/2024

Localisation: Laboratoire de Chimie de Coordination (LCC-CNRS)
205, route de Narbonne
31400 Toulouse


This research master's degree project could be followed by a PhD

Work package:
In the context of sustainable development, it is now essential to consider the recovery and recycling of catalysts in order to improve energy efficiency, limit environmental impact and lower the cost of catalytic processes, especially when rare metals or expensive ligands, like enantiomerically pure ones, are involved. Micellar biphasic catalysis between an aqueous phase and an organic phase thus offers a very interesting solution but suffers from several disadvantages, such as swelling of the micelle by the solvents/reagents, which can lead to the formation of stable emulsions, preventing good recycling. A very promising solution is to develop "core-shell" nanoreactors first by controlled polymerisation-induced self-assembly (PISA) to obtain micelle of controlled size and finally cross-linking of all branches of the micelles. The nanoreactors obtaines by this methodology are composed of a hydrophobic core (cross-linked in the centre) where the catalysts are located and a hydrophilic peripheral layer ensuring solubilisation in water.[1] They have been used in various metal-catalyzed reactions like hydroformylation and hydrogenation. [1] The aim of this project is to apply this methodology to organocatalysis, which have both proven to be very powerful tools for the synthesis of organic compounds.[2] Some nanoreactors containing phosphines[1] are already available and will be tested first in organocatalyzed reactions. Some new nanoreactors containing other organocatalysts like amines or chiral phosphines should also be synthesized and tested again in organocatalyzed reactions. This multi-disciplinary internship will provide skills in organic chemistry, catalysis and polymerisation. This multifaceted subject will call upon various characterisation techniques such as multinuclear and multi-dimensional NMR, mass spectrometry, dynamic light scattering (DLS), transmission electron microscopy (TEM)

[1] (a) X. Zhang, A. F. Cardozo, S. Chen, W. Zhang, C. Julcour, M. Lansalot, J.F. Blanco, F. Gayet, H. Delmas, B. Charleux, Chem.-Eur. J. 2014, 20, 15505 ; (b) E. Lobry, A. Cardozo, L. Barthe, J. F. Blanco, H. Delmas, S. Chen, F. Gayet, X. Zhang, M. Lansalot, F. d’Agosto, R. Poli, E. Manoury, C. Julcour, J. Catal. 2016, 164, 172 ; (c) A. Joumaa, F. Gayet, E. J. Garcia-Suarez, J. Himmelstrup, A. Riisager, R. Poli, E. Manoury, Polymers, 2020, 12, 1107. (d) S. S. Sambou, R. Hromov, I. Ruzhylo, H. Wang, A. Allandrieu, C. Sabatier, Y. Coppel, J.-C. Daran, F. Gayet, A. Labande, E. Manoury, R. Poli, Catal. Sci. Technol. 2021, 11, 6811-6824. (d) H. Wang, C. J. Abou-Fayssal, C. Fliedel, E. Manoury, R. Poli, Polymers, 2022, 14, 4937. [2] (a) M. P. van der Helm, B. Klemm, R. Eelkema Nature Rev. Chem. 2019, 491-508; (b) D. L. Org. Process Res. Dev. 2018, 22, 574−584; (c) the importance of asymmetric organocatalysis has been recognized by the award of the Nobel Prize in Chemistry to David W. C. McMillan and B. List for their works on asymmetric catalysis.

Areas of expertise:
ligand synthesis, polymerization, homogeneous catalysis, asymmetric catalysis, chromatography

Required skills for the internship:
We are looking for a dynamic, curious and motivated student, with a strong interest for organic chemistry and catalysis; knowledge in polymerization techniques would be a plus.