Metallomimetic C-F activation catalysis by simple phosphines - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 2024

Metallomimetic C-F activation catalysis by simple phosphines

Résumé

Delivering metallomimetic reactivity from simple p-block compounds is highly desirable in the search to replace expensive, scarce precious-metals by cheap and abundant elements in catalysis. This contribution demonstrates that metallomimetic catalysis, involving facile redox cycling between the P(III) and P(V) oxidation states, is possible using only simple, cheap and readily available trialkylphosphines with no need for complex ligand architectures or external oxidising/reducing agents. Hydrodefluorination and aminodefluorination of a range of fluoroarenes was realised with good to very good yields under mild conditions. Experimental and computational mechanistic studies show that the phosphines undergo oxidative addition of the fluoroaromatic substrate, via a Meisenheimer-like transition state, to form a fluorophosphorane. This undergoes a pseudo-transmetallation step with a silane, via initial fluoride transfer from P to Si, to give experimentally observed phosphonium ions. Hydride transfer from a hydridosilicate counterion then leads to a hydridophosphorane, which undergoes reductive elimination of the product to re-form the phosphine catalyst. This behaviour is analogous to many classical transition-metal catalysed reactions and so is a rare example of both functional and mechanistically metallomimetic behaviour in catalysis by a main-group element system. Crucially, the reagents used are cheap, readily available commercially and easy to handle, making these reactions a realistic prospect in a wide range of academic and industrial settings.
Fichier principal
Vignette du fichier
Bonafante, Metallomimetic C−F Activation Catalysis, 2024.pdf (1.84 Mo) Télécharger le fichier
Origine : Publication financée par une institution
Licence : CC BY - Paternité

Dates et versions

hal-04269048 , version 1 (03-11-2023)
hal-04269048 , version 2 (26-01-2024)

Licence

Paternité

Identifiants

Citer

Sara Bonfante, Christian Lorber, Jason M Lynam, Antoine Simonneau, John M Slattery. Metallomimetic C-F activation catalysis by simple phosphines. Journal of the American Chemical Society, 2024, 146 (3), pp.2005-2014. ⟨10.1021/jacs.3c10614⟩. ⟨hal-04269048v2⟩
71 Consultations
34 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More