Unnatural Amino Acid Synthesis Enabled by the Regioselective Cobalt(III)-Catalyzed Intermolecular Carboamination of Alkenes.

Herein, we report an unprecedented regioselective and entirely atom-economic cobalt(III)-catalyzed method for the non-annulative, intermolecular carboamination of alkenes. The methodology enables the direct synthesis of unnatural amino acid derivatives and proceeds under redox-neutral conditions with a completely regioselective C-C bond and C-N bond formation. Furthermore, this reaction exemplifies the inherently different mechanistic behavior of the Cp*Co catalyst and its Cp*Rh counterpart, especially towards β-H-elimination.