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

Abstract

A new class of chiral cyclopentadienyl rhodium(I) complexes (CpRh^I ) bearing C₂ -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.

Keywords: C−H activation; asymmetric catalysis; ligand design; rhodium; synthetic methods.