Engineering of Dual-Function VitreoscillaHemoglobin: A One-Pot Strategy for the Synthesis of Unnatural α-Amino Acids

Despite a well-developed and growing body of work on the directed evolution of hemoproteins, the potential of hemoproteins to catalyze non-natural reactions remains underexplored. This paper reports a new biocatalytic strategy for the one-pot synthesis of unnatural α-amino acids. Engineered variants of dual-function Vitreoscillahemoglobin were found to efficiently catalyze N–H insertion and C–H sp3alkylation, providing moderate to excellent yields (57%–95%) of unnatural α-amino acid derivatives and turnover numbers (1425–2375).