To address these limitations, we evaluated our PpMPC azidase and thiocyanase evolutionary lineage for our targeted radical isocyanation reaction. In the early stage of this research, it was found that the radical rebound product alkylisocyanate (R-N=C=O, 7) underwent rapid hydrolysis in the aqueous buffer. This provided the corresponding alkylamine as the end product, due to the rapid decarboxylation of the carbamic acid resulting from the nucleophilic addition of water to the alkylisocyanate 7. To circumvent this problem, we evaluated a range of nucleophiles as the trapping reagent to intercept the enzymatically generated enantioenriched organic isocyanate product 7. After extensive optimization, aniline (Ph) was identified as an appropriate isocyanate trapping agent. The appropriate nucleophilicity of aniline allowing the rapid interception of the incipient alkylisocyanate but not the N-hydroxyphthalimide ester substrate represented the key to resolving this challenge. Furthermore, using aniline as the trapping agent, this chemoenzymatic cascade afforded unsymmetrical urea product 8 in 20% yield with an excellent enantiomeric ratio of 98:2. Scheme 2. Photometallobiocatalytic Enantioconvergent Decarboxylative Isocyanation/Unsymmetrical Urea Formation.