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Mechanistic Insights about the Ligand‐Enabled Oxy‐arylation/vinylation of Alkenes via Au(I)/Au(III) Catalysis
Author(s) -
Rigoulet Mathilde,
Miqueu Karinne,
Bourissou Didier
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202202110
Subject(s) - regioselectivity , nucleophile , chemistry , catalysis , ligand (biochemistry) , reactivity (psychology) , reaction mechanism , medicinal chemistry , stereochemistry , computational chemistry , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology
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.