LAUSR

Transition metal-catalyzed cross-electrophile coupling (XEC) is a powerful tool for forging C(sp2)-C(sp2) bonds in biaryl molecules from abundant aromatic halides. While syntheses of unsymmetrical biaryl compounds through multimetallic XEC is of high synthetic value, selective XEC of two heteroaromatic halides remains elusive and challenging. Herein we report a homogeneous XEC method which relies on a zirconaaziridine complex as a shuttle for dual palladium catalyzed processes. The zirconaaziridine-mediated palladium (ZAPd) catalyzed reaction shows excellent compatibility with various functional groups and diverse heteroaromatic scaffolds. In accord with density functional theory (DFT) calculations, a redox-transmetallation between the oxidative addition product and the zirconaaziridine is proposed as the crucial elementary step. Thus, cross-coupling selectivity using a single transition metal catalyst is controlled by the relative rate of oxidative addition of Pd(0) into the aromatic halide. Overall, the concept of a combined reducing and transmetallating agent offers opportunities for development of transition-metal reductive coupling catalysis.