Enantioselective Tethered Counterion-Directed Catalysis – TCDCat

The necessity to access chiral molecules by targeting a given enantiomer is of utmost importance. As a result, transition metal catalysis with complexes bearing chiral ligands has become the best ally of synthetic chemists. This ligand-based approach often relies on the use of highly bulky ligands to trigger steric repulsions influencing transition state geometry during a given enantiodetermining step. The alternative Asymmetric Couteranion-Directed Catalysis approach features both steric effects and non-covalent interactions. However, 15 years later, the field did not bloom as much as expected. This probably results from poorly defined and flexible special arrangements of the chiral phosphate-cation pairs. In this context, we established that tethering the chiral anion to the metal center would afford geometrical constraints and molecular organization to the intermediates involved in catalytic processes to generate high enantioselectivities.

The TCDCat project intends to develop and establish the Tethered Counterion-Directed Strategy as an unavoidable strategy in enantioselective transition metal catalysis. In this purpose, the project will tackle the synthesis of novel bifunctional complexes of various transition metal and the application of these complexes as chiral catalysts in enantioselective reactions involving remote-to-metal cationic intermediates.