Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly Enantioselective 3d-Metal-Catalyzed C-H Functionalizations.

The synthesis of a set of cobalt(III)-complexes equipped with trisubstituted chiral cyclopentadienyl ligands is reported, and their steric and electronic parameters are mapped. The application potential of these complexes for asymmetric C-H functionalizations with 3d-metals is shown by the synthesis of dihydroisoquinolones from N-chlorobenzamides with a broad range of alkenes. The transformation proceeds with excellent enantioselectivities of up to 99.5:0.5 er and high regioselectivities. The observed values outperform the best rhodium(III)-based methods for this reaction type. Moreover, challenging substrates such as alkyl alkenes also react with high regio- and enantioselectivities.