(P,C) Cyclometalated Gold(III) Complexes: Highly Active Catalysts for the Hydroarylation of Alkynes

The first catalytic application of well‐defined (P,C) cyclometalated gold(III) complexes is reported. The bench‐stable bis(trifluoroacetyl) complexes 2 a,b perform very well in the intermolecular hydroarylation of alkynes. The reaction is broad in scope, it proceeds within few hours at 25 °C at catalytic loadings of 0.1–5 mol %. The electron‐rich arene adds across the C≡C bond with complete regio‐ and stereo‐selectivity. The significance of well‐defined gold(III) complexes and ligand design are highlighted in a powerful but challenging catalytic transformation. Yes, AuIII can do it and the ancillary ligand counts! The first catalytic application of (P,C) cyclometalated gold(III) complexes shows they perform very well in the hydroarylation of alkynes, surpassing all known gold catalysts. They give high regio‐ and stereoselectivity with a broad substrate scope.