Chiral Bicyclo[2.2.2]octane‐Fused CpRh Complexes: Synthesis and Potential Use in Asymmetric C−H Activation

A new class of chiral cyclopentadienyl rhodium(I) complexes (CpRh I ) bearing C 2 ‐symmetric chiral bridged‐ring‐fused Cp ligands was prepared. The complexes were successfully applied to the asymmetric C−H activation reaction of N ‐methoxybenzamides with quinones, affording a series of chiral hydrophenanthridinones in up to 82 % yield with up to 99 % ee . Interestingly, structure analysis reveals that the side wall of the optimal chiral CpRh I catalyst is vertically more extended, horizontally less extended, and closer to the metal center in comparison with the classic binaphthyl and spirobiindanyl CpRh I complexes, and may thus account for its superior catalytic performance.