A Mn(salen)‐Based Artificial Metalloenzyme for Nitrene and Oxene Transfer Catalysis

Abstract The development of artificial metalloenzymes (ArMs) offers a potent approach to incorporate non‐natural chemical reactions into biocatalysis. Here we report the assembly of Mn(salen)‐based ArMs by embedding biotinylated Mn(salen) complexes into streptavidin (Sav) variants. Using commercially available nitrene and oxo transfer reagents, these biohybrid catalysts catalyzed the aziridination of alkenes and oxidation of benzylic C−H bonds with up to 19 and 146 turnover numbers.