Mechanistic Insights about the Ligand‐Enabled Oxy‐arylation/vinylation of Alkenes via Au(I)/Au(III) Catalysis

Mathilde Rigoulet (1) , Karinne Miqueu (2) , Didier Bourissou (1)

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

The mechanism of oxy-arylation/vinylation of alkenes catalyzed by the (MeDalphos)AuCl complex was comprehensively investigated by DFT. (P,N)Au(Ph) 2 + and (P,N)Au(vinyl) 2 + are key intermediates accounting for the activation of the alkenols and for their cyclization by outersphere nucleophilic attack of oxygen. The 5-exo and 6-endo paths have been computed and compared, reproducing the peculiar regioselectivity difference observed experimentally between 4-penten-1-ol, (E) and (Z)-4-hexen-1-ols. Examining the way the alkenol coordinates to gold (more η 2 or η 1) can offer, in some cases, a simple way to predict the favored path of cyclization.

Mots clés: complexdensity; ·functional theory; ·gold; ·mechanism; ·regioselectivity

Domaines: Chimie; Matériaux; Chimie théorique et/ou physique

Mathilde Rigoulet, Karinne Miqueu, Didier Bourissou. Mechanistic Insights about the Ligand‐Enabled Oxy‐arylation/vinylation of Alkenes via Au(I)/Au(III) Catalysis. Chemistry - A European Journal, 2022, pp.e202202110. ⟨10.1002/chem.202202110⟩. ⟨hal-03781154⟩