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