Consolidation of the Oxidant‐Free Au (I)/Au (III) Catalysis Enabled by the Hemilabile Ligand Strategy

Abstract: In this minireview we survey the challenges and strategies in gold redox catalysis. Gold's reluctance to oxidative addition reactions due to its high redox potential limits its applicability. Initial attempts to overcome this problem focused on the use of sacrificial external oxidants in stoichiometric amounts to bring Au (I) compounds to Au (III) reactive species. Recently, innovative approaches focused on employing hemilabile ligands, which are capable of coordinating to Au (I) and stabilizing square‐planar Au (III) intermediates, thus facilitating oxidative addition steps and enabling oxidant‐free catalysis. Notable examples include the use of the (P^N) bidendate MeDalphos ligand to achieve various cross‐coupling reactions via oxidative addition Au (I)/Au (III). Importantly, hemilabile ligand‐enabled catalysis allows merging oxidative addition with π‐activation, such as oxy‐ and aminoarylation of alkenols and alkenamines using organohalides, expanding gold‘s versatility in C−C and C‐heteroatom bond formations and unprecedented cyclizations. Moreover, recent advancements in enantioselective catalysis using chiral hemilabile (P^N) ligands are also surveyed. Strikingly, versatile bidentate (C^N) hemilabile ligands as competitors of MeDalphos have appeared recently, by designing scaffolds where phosphine groups are substituted by N‐heterocyclic or mesoionic carbenes. Overall, these approaches highlight the evolving landscape of gold redox catalysis and its tremendous potential in a broad scope of transformations.

Location
Deutsche Nationalbibliothek Frankfurt am Main
Extent
Online-Ressource
Language
Englisch

Bibliographic citation
Consolidation of the Oxidant‐Free Au (I)/Au (III) Catalysis Enabled by the Hemilabile Ligand Strategy ; day:14 ; month:05 ; year:2024 ; extent:19
Angewandte Chemie / International edition. International edition ; (14.05.2024) (gesamt 19)

Creator
Font, Pau
Valdés, Hugo
Ribas, Xavi

DOI
10.1002/anie.202405824
URN
urn:nbn:de:101:1-2405151425287.044430392203
Rights
Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
Last update
14.08.2025, 11:01 AM CEST

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