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

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 outer‐sphere 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.