Gold-Catalyzed Oxidative Biaryl Cross-Coupling of Organometallics

The biaryl coupling between a nucleophile (Ar delta-: arylboronates or arylsilanes) and an electrophile (Ar delta+: arylhalides) represents the state of the art in carbon-carbon bond formation. The intrinsic functional-group limitations in these reactions stem from the high catalytic reactivity of palladium and nickel catalysts toward halogen, boronate, and base-sensitive substituents. Here, we report a general dimeric gold-catalyzed oxidative cross-coupling of arylboronates and arylsilanes without an external base for the synthesis, with excellent functional-group tolerance of asymmetric biaryls. Both coupling partners are readily available, bench-stable, and non-toxic A broad array of (pseudo)halogenated and borylated coupling partners can be successfully applied to this site-specific biaryl coupling with unprecedented versatility. Its synthetic value has been substantiated by concise preparation of several pi-conjugated organic materials and pharmacophores.