A Class of Readily Tunable Planar-Chiral Cyclopentadienyl Rhodium(III) Catalysts for Asymmetric C-H Activation.

Chiral half-sandwich cyclopentadienyl rhodium(III) (CpRh ) complexes are powerful catalysts for promoting asymmetric C-H activation reactions. Their preparation normally involved linking or embedding the Cp motif to or into a certain chiral backbone to forge the so-called chiral Cp ligand. However, preparation of a planar-chiral CpRh catalyst bearing a non-chiral Cp ligand remains a formidable challenge and is rarely reported. We describe herein an unusual class of planar-chiral rhodium catalysts bearing non-chiral Cp ligands. Different from existing ones, this catalyst is readily tunable. Ten planar-chiral only CpRh catalysts were prepared with ease, and successfully used in two enantioselective C-H activation reactions. Given its convenient synthesis and high structural tunability, these catalysts are expected to find more utilities in asymmetric C-H activation.