Gold-Catalyzed Oxidative Biaryl Cross-Coupling of Organometallics

Summary The biaryl coupling between a nucleophile (Arδ−: arylboronates or arylsilanes) and an electrophile (Arδ+: 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 π-conjugated organic materials and pharmacophores.