Au(I)/Au(III) Catalytic Allylation Involving π-Allyl Au(III) Complexes

Jessica Rodriguez , David Vesseur , Alexis Tabey , Sonia Mallet-Ladeira , Karinne Miqueu (1) , Didier Bourissou (2)

1 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
2 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée

A (MeDalphos)AuCl complex was found to efficiently catalyze the cross-coupling of indoles and allyl acetates/alcohols. The reaction tolerates many functional groups and selectively affords the branched C3-allylated products from both α- and γ-substituted allyl substrates. It takes the advantage of the hemilabile character of the P∧N ligand. The C(sp2)-C(sp3) coupling operates via a Au(I)/Au(III) redox cycle and involves a dicationic π-allyl Au(III) complex as a key intermediate. In this case, the allyl moiety adopts an asymmetric σ + π-coordination mode, as substantiated by NMR spectroscopy and density functional theory (DFT) calculations.

Mots clés: (P∧N) ligands; gold; homogeneous catalysis; indoles; π-allyl

Domaines: Chimie

Jessica Rodriguez, David Vesseur, Alexis Tabey, Sonia Mallet-Ladeira, Karinne Miqueu, et al.. Au(I)/Au(III) Catalytic Allylation Involving π-Allyl Au(III) Complexes. ACS Catalysis, 2022, 12 (2), pp.993-1003. ⟨10.1021/acscatal.1c04580⟩. ⟨hal-03543277⟩