Cobalt(III)-Catalyzed Enantioselective Intermolecular Carboamination by C-H Functionalization.

High-valent cyclopentadienyl cobalt catalysis is a versatile tool for sustainable C-H bond functionalizations. To harness the full potential of this strategy, control of the stereoselectivity of these processes is necessary. Herein, we report highly enantioselective intermolecular carboaminations of alkenes through C-H activation of N-phenoxyamides catalyzed by CoIII -complexes equipped with chiral cyclopentadienyl (Cpx ) ligands. The method converts widely available acrylates as well as bicyclic olefins into attractive enantioenriched isotyrosine derivatives as well as elaborated amino-substituted bicyclic scaffolds under very mild conditions. The outlined reactivity is unique to the Cpx CoIII complexes and is complementary to the reactivity of 4d- and 5d- precious-metal catalysts.