Chiral Cyclopentadienyl Iridium(III) Complexes Promote Enantioselective Cycloisomerizations Giving Fused Cyclopropanes

The cyclopentadienyl (Cp) group is a very important ligand for many transition‐metal complexes which have been applied in catalysis. The availability of chiral cyclopentadienyl ligands (Cp x ) lags behind other ligand classes, thus hampering the investigation of enantioselective processes. We report a library of chiral Cp x Ir III complexes equipped with an atropchiral Cp scaffold. A robust complexation procedure reliably provides Cp x Ir III complexes with tunable counterions. In a proof‐of‐concept application, the iodide‐bearing members are shown to be highly selective for enyne cycloisomerization reactions. The dehydropiperidine‐fused cyclopropane products are formed in good yields and enantioselectivities.