Bifunctional Ligand Enables Gold‐Catalyzed Propargyl C‐H Functionalization via Reactive Gold Allenylidene Intermediate

Abstract Gold allenylidene species have been seldom exploited as reactive intermediates in synthetically versatile catalytic reactions. By employing alkynylbenziodoxoles as the substrates and bifunctional WangPhos as the metal ligand, this work demonstrated ready catalytic access to these intermediates of general substitution patterns and their electrophilic reactivities at the γ‐carbon center with a diverse range of nucleophiles. The reaction is driven by the reductive decomposition of the benziodoxole moiety and achieves the replacement of a propargylic proton with an N/O/C‐based nucleophile, hence realizing reactivity umpolung. Corroborated by Density Functional Theory (DFT) calculations, the reaction mechanism involves a mild propargylic deprotonation. In contrast to prior works employing a tertiary amine functionality, a weakly BrØnsted‐basic amide group in WangPhos is surprisingly effective in deprotonation at the propargylic position under a gold‐ligand cooperation regime.