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

AbstractThe 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 outer‐sphere nucleophilic attack of oxygen. The 5‐exoand 6‐endopaths 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 η2or η1) can offer, in some cases, a simple way to predict the favored path of cyclization.