Iridium(I)-Catalyzed Asymmetric Intermolecular Hydroarylation of Norbornene with Benzamide

 Starting from the dinuclear chloro-bridged Ir(I) complexes IrCl(PP)]₂ (PP = (R)-(6,6′-dimethylbiphenyl-2,2′-diyl)-1,1′-bis-(diphenylphosphine), (R)-(6,6′-dimethoxy-biphenyl-2,2′-diyl)-1,1′-bis-(diphenylphosphine), and (R)-1-((S)-2-(diphenylphosphino-ferrocenyl))-ethyldicyclohexylphosphine), a new class of cyclopentadienyl Ir(I) complexes containing a chiral bisphosphine (IrCp(PP)]) was prepared and characterized. These new complexes are suited precatalysts for the direct hydroarylation of norbornene with benzamide. 2-(exo-Norbornyl)-benzamide is formed with an enantiomeric excess of up to 94% by the use of 1 mol% iridium, albeit in low yield.