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2.Supramolecular catalysis

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The performance (activity, selectivity, stability) of classical homogeneous catalysts is difficult to modulate since these catalysts possess a covalent backbone. Supramolecular polymers, such as mentioned above, constitute an interesting platform for the preparation of innovative catalysts. These catalysts are dynamic (based on hydrogen bonds), functionalizable (by chemcial modification of the monomers) and reversible (their architecture varies according to the concentration, the temperature among other parameters). By means of these unique properties, we want to demonstrate that the self-association can be used to modulate the electronic, steric and chiral environments of a catalytic site. As a proof-of-concept, we showed that the enantioselectivity of a rhodium catalyst can be modulatd by mixing benzene 1,3,5-tricarboxamide (BTA) monomers able to self-associate into chiral helices in solution.

For more information, see :
“Tunable asymmetric catalysis through ligand stacking in chiral rigid rods” M. Raynal, F. Portier, P. W. N. M. van Leeuwen, L. Bouteiller J. Am. Chem. Soc. 2013, 135, 17687-17690.
"Correlation between the selectivity and the structure of an asymmetric catalyst built on a chirally amplified supramolecular helical scaffold" A. Desmarchelier, X. Caumes, M. Raynal, A. Vidal-Ferran, P. W. N. M. van Leeuwen, L. Bouteiller J. Am. Chem. Soc. 2016, 138, 4908-4916.