We reasoned that through directed evolution, we could engineer highly stereoselective nonheme Fe enzymes to allow the enantioconvergent decarboxylative azidation of racemic redox-active esters, leading to valuable secondary-and tertiary-alkyl azides in a highly enantioenriched form. Furthermore, as nonheme Fe enzymes could potentially bind other anions including thiocyanate (SCN -) and cyanate (OCN -), we envisioned that through the identification and engineering of suitable nonheme Fe enzyme scaffolds, we could generalize this strategy and accomplish enantioselective radical thiocyanation and isocyanation. Due to the synthetic versatility of organic azides, thiocyanates and isocyanates and a variety of previously established transformations associated with these building blocks, our photometallobiocatalytic azidation, thiocyanation and isocyanation methods would provide a powerful means to the asymmetric synthesis of valuable molecular entities.