This study describes a general chemoselective Suzuki–Miyaura coupling of polyhalogenated aryl triflates with the reactivity order of C–Cl > C–OTf using a Pd/L33 catalyst. The methine hydrogen and the steric hindrance offered by the alkyl bottom ring of L33 were found to be key factors in reactivity and chemoselectivity. With the Pd/L33 catalyst, a wide range of polyhalogenated (hetero)­aryl triflates, which were independent of the substrates and of the relative positioning of the competing reaction sites, coupled well with (hetero)­aryl, alkenyl, and alkylboronic acids to obtain the corresponding products with good chemoselectivity and yields. The chemoselective reaction could easily be scaled up to the gram scale, and the use of parts per million levels of Pd catalyst (as low as 10 ppm Pd) was achieved.

This study reports the palladium-catalyzed chemoselective borylation of (poly)halogenated aryl triflates with a reactivity order of CÀ Cl > CÀ OTf. A catalyst system comprising Pd(OAc) 2 and SelectPhos (L1) enables a reaction with high reactivity and chemoselectivity. The consecutively chemoselective borylation reaction followed by the chemoselective intermolecular Suzuki-Miyaura reaction can be performed using a one-pot two-step approach to synthesize unsymmetrical biaryl compounds containing the triflate moiety. The reaction can be scaled up to the gram scale without diminishing the yield and chemoselectivity.

This article presents a comprehensive analysis of the progress in palladium-catalyzed coupling reactions, with an emphasis on how ligand characteristics affect the chemoselectivity of aryl (pseudo)halides.

A novel family of indole-amide-based phosphine ligands was designed and synthesized.