Rapid Room-Temperature, Chemoselective Csp2−Csp2Coupling of Poly(pseudo)halogenated Arenes Enabled by Palladium(I) Catalysis in Air

Abstract

While chemoselectivities in Pd0-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 PdIthat allows for an a priori predictable chemoselective Csp2−C Csp2coupling 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 PdIdimer under open-flask conditions.