Nitrene Transfer Catalyzed by a Non-Heme Iron Enzyme and Enhanced by Non-Native Small-Molecule Ligands

Transition-metal catalysis is a powerful tool for the
construction
of chemical bonds. Here we show that Pseudomonas savastanoi ethylene-forming enzyme, a non-heme iron enzyme, can catalyze olefin
aziridination and nitrene C–H insertion, and that these activities
can be improved by directed evolution. The non-heme iron center allows
for facile modification of the primary coordination sphere by addition
of metal-coordinating molecules, enabling control over enzyme activity
and selectivity using small molecules.