Conférence Dr Xavier GUINCHARD

Dr Xavier GUINCHARD

Université Paris-Saclay, CNRS, Institut de Chimie des Substances Naturelles (ICSN), UPR2301, 91198 Gif-sur-Yvette, France.

CPAPhosAuCl chiral complexes in enantioselective (multi) catalysis

The access to enantioenriched molecules via selective catalytic methods is of utmost importance. The Asymmetric Counteranion-Directed Catalysis (ACDC) approach1 relies on the use of chiral counteranions as the source of stereochemical information during the key bond- forming step. The strong pairing between the cationic metal-substrate complex and the chiral anion is hence central to the transfer of the chiral information. This concept,1a pioneered in Au(I)1c and Pd(0)1a catalysis, was rapidly applied to other transition metals. However, almost 20 years later, the field did not bloom as much as expected and examples remain sporadic. This probably results from the flexible and poorly defined spatial arrangements of the chiral phosphate-cation pairs.

In this context, we have established that tethering the chiral anion to the metal center could be a suitable strategy to increase geometrical constraints and molecular organization in the intermediates involved in catalytic processes and therefore generate higher enantioselectivities. This strategy, named Tethered Counterion-Directed Catalysis (TCDC) relies on the development and use of CPAPhos chiral ligands that are phosphine/phosphoric acid new chiral bifunctional ligands.2a The corresponding Au(I) complexes have been prepared and used successfully as catalysts in a number of enantioselective reactions.2

The use of these new chiral complexes in a range of different catalytic applications  in enantioselective Au(I) catalysis2 –and beyond- will be described.

Références

[1] (a) Mahlau, M.; List, B. Angew. Chem. Int. Ed. 2013, 52, 518; (b) Hamilton, G. L.; Kang, E. J.; Mba, M.; Toste, F. D. Science 2007, 317, 496; (c) Zi, W.; Toste, D. F. Chem. Soc. Rev. 2016, 45, 4567.

[2] (a) Zhang, Z.; Smal, V.; Retailleau, P.; Voituriez, A.; Frison, G.; Marinetti, A.; Guinchard, X. J . Am. Chem. Soc . 2020, 142, 3797. (b) Yu, Y.; Zhang, Z.; Voituriez, A.; Rabasso, N.; Frison, G.; Marinetti, A.; Guinchard, X. Chem. Commun. 2021, 57, 10779. (c) Zhang, Z.; Sabat, N.; Frison, G.; Marinetti, A.; Guinchard, X. ACS Cat al. 2022, 12, 4046. (d) Yu, Y.; Sabat, N.; Daghmoum, M.; Zhang, Z.; Retailleau, P.; Frison, G.; Marinetti, A.; Guinchard, X. Org. Chem. Front . 2023, 10, 2936. (e) Xu, H.; Zhang, Z.; Marinetti, A.; Guinchard, X., Org. Lett. 2024, 26, 9525.