Rapid Room‐Temperature, Chemoselective C [Formula: see text] −C [Formula: see text] Coupling of Poly(pseudo)halogenated Arenes Enabled by Palladium(I) Catalysis in Air

While chemoselectivities in Pd(0)‐catalyzed coupling reactions are frequently non‐intuitive and a result of a complex interplay of ligand/catalyst, substrate, and reaction conditions, we herein report a general method based on Pd(I) that allows for an a priori predictable chemoselective C [Formula: see text] −C [Formula: see text] coupling at C−Br in preference to C−OTf and C−Cl bonds, regardless of the electronic or steric bias of the substrate. The C−C bond formations are extremely rapid (<5 min at RT) and are catalyzed by an air‐ and moisture‐stable Pd(I) dimer under open‐flask conditions.