Palladium-catalyzed chemoselective decarboxylative coupling of alkynyl carboxylic acids with halogenated aryl triflates

Abstract

A palladium-catalyzed chemoselective decarboxylative coupling of alkynyl carboxylic acids with halogenated aryl triflates has been developed for the efficient synthesis of OTf-arylalkyne scaffolds. Notably, this transformation exhibits an inversion of the conventional chemoselectivity order, favoring C-Br > C-Cl > C-OTf. In addition, a one-pot sequential strategy was established by integrating the decarboxylative coupling with a Suzuki-Miyaura reaction, offering a versatile platform for the synthesis of difunctionalized aromatic compounds. Density functional theory (DFT) calculations indicate that the oxidative addition step governs the chemoselectivity, while the decarboxylation step is proposed to be rate-determining.