Palladium-catalyzed chemoselective Suzuki–Miyaura cross-coupling reaction of poly(pseudo)halogenated arenes

This paper presents general examples of the palladium-catalyzed chemoselective Suzuki–Miyaura cross-coupling reaction of polyhalogenated aryl triflates with a reactivity order of C–Br > C–Cl > C–OTf. A diverse array of bromo(hetero)aryl triflates was successfully coupled with (hetero)aryl boronic acids, achieving excellent reactivity and chemoselectivity. This was accomplished using a catalyst system composed of Pd(OAc)₂ and SelectPhos (L1), with catalyst loadings reducible to as low as 0.02 mol% Pd. The sequential double functionalization of bromochloroaryl triflates was also demonstrated successfully, paving the way for the synthesis of terphenyl derivatives.