Gold-catalysed Heck reaction: Fact or fiction? Correspondence on “Unlocking the Chain Walking Process in Gold Catalysis”

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Budzelaar, Peter H. M., Bochmann, Manfred ORCID: https://orcid.org/0000-0001-7736-5428, Landrini, Martina and Rocchigiani, Luca (2024) Gold-catalysed Heck reaction: Fact or fiction? Correspondence on “Unlocking the Chain Walking Process in Gold Catalysis”. Angewandte Chemie-International Edition, 63 (47). ISSN 1433-7851

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Abstract

Two recent high-profile publications reported the formation of Heck-type arylated alkenes catalysed by MeDalPhosAuCl / AgOTf (J. Am. Chem. Soc. 2023, 145, 8810) and their cyclisation to tetralines (Angew. Chem. Int. Ed. 2023, e202312786). It was claimed that these were the first demonstrations in gold catalysis of alkene insertion into Au-aryl bonds, β-H elimination and chain-walking by Au-H dications. We show here that in fact this chemistry is a two-stage process. Only the first step, the production of an alkyl triflate ester as the primary organic product by the well-known alkene heteroarylation sequence, involves gold. The subsequent formation of Heck-type olefins and their cyclisation to tetralines represent classical H+-triggered carbocationic chemistry. These steps proceed in the absence of gold with identical results. Literature claims of new gold reactivity such as chain walking by the putative [LAuH]2+ dication have no basis in fact.

Item Type: Article
Additional Information: Data Availability Statement: The data that support the findings of this study are available in the supplementary material of this article. Funding information: Royal Society of Chemistry. Grant Number: R22-0875640255
Uncontrolled Keywords: carbocations,gold catalysis,heck reaction,heteroarylation,mechanisms,nmr,chemistry(all),catalysis ,/dk/atira/pure/subjectarea/asjc/1600
Faculty \ School: Faculty of Science > School of Chemistry (former - to 2024)
UEA Research Groups: Faculty of Science > Research Groups > Chemistry of Light and Energy
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Depositing User: LivePure Connector
Date Deposited: 13 May 2024 12:30
Last Modified: 18 Nov 2024 04:30
URI: https://ueaeprints.uea.ac.uk/id/eprint/95124
DOI: 10.1002/anie.202317774

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