Abstract

AbstractHigh‐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 CpxCoIII complexes and is complementary to the reactivity of 4d‐ and 5d‐ precious‐metal catalysts.

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