Gold‐Catalysed Heck Reaction: Fact or Fiction? Correspondence on “Unlocking the Chain Walking Process in Gold Catalysis”

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.