Oxidant speciation and anionic ligand effects in the gold-catalyzed oxidative coupling of arenes and alkynes†
The mechanism of the gold-catalyzed oxidative cross-coupling of arenes and alkynes has been studied in detail combining stoichiometric experiments with putative reaction intermediates and DFT calculations. Our data suggest that ligand exchange between the alkyne, the Au(I)-catalyst and the hypervalent iodine reagent is responsible for the formation of both an Au(I)-acetylide complex and a more reactive “non-symmetric” I(III) oxidant responsible for the crucial Au(I)/Au(III) turnover. Further, the reactivity of the in situ generated Au(III)-acetylide complex is governed by the nature of the anionic ligands transferred by the I(III) oxidant: while halogen ligands remain unreactive, acetato ligands are efficiently displaced by the arene to yield the observed Csp2–Csp cross-coupling products through an irreversible reductive elimination step. Finally, the nature of competitive processes and catalyst deactivation pathways has also been unraveled. This detailed investigation provides insights not only on the specific features of the species involved in oxidative gold-catalyzed cross couplings but also highlights the importance of both ancillary and anionic ligands in the reactivity of the key Au(III) intermediates.
- This article is part of the themed collections: Most popular 2019-2020 organic chemistry articles, Editor’s Choice – Ning Jiao, New reactivity in organic chemistry and Editor's choice - Paolo Melchiorre