With efficient nonheme enzymes for enantioconvergent radical azidation, we carried out the further engineering of PpMPC to catalyze the asymmetric decarboxylative thiocyanation of redox-active esters (Table ). In contrast to enantioselective azidation, in the current thiocyanation process, irradiating at 525 nm with green LED provided better results compared to that at 440 nm. Although the nonheme Fe enzyme system showed lower levels of activity towards radical thiocyanation relative to azidation, we found that the PpMPC evolutionary lineage we gathered in the development of catalytic asymmetric azidation described above also showed steady improvement in activity or enantioselectivity for the present catalytic thiocyanation. Specifically, PpMPC I291L displayed a 2.2-fold improvement in activity relative to the wild-type PpMPC (Table , entries 1 and 2). The inclusion of L155F to PpMPC I291L substantially enhanced its enantiocontrol over radical thiocyanation, allowing 5a to form in 42% yield and 94:6 e.r. (entry 3). Starting from PpMPC I291L L155F, an additional round of SSM and screening furnished a new triple mutant PpMPC I291L L155F I204L, allowing the conversion of (rac)-1a into thiocyanation product 5a in 54% yield and 95:5 e.r. (entry 4). With the triple mutant radical thiocyanase PpMPC I291L L155F I204L, we briefly surveyed the substrate scope of this dual photobiocatalytic asymmetric radical thiocyanation (Table ). It was found that secondary alkyl radicals were compatible with this photobiocatalytic protocol. N-hydroxyphthalimide esters possessing a methyl group at the ortho-(5b) and meta-(5c) positions were converted with excellent enantiocontrol. Substrates with a para-chlorine (5d) para-bromine (5e), meta-methoxy (5f) group as well as a 4-chloro-3-fluoro substrate (5g) could also be successfully transformed into the corresponding thiocyanated product with good to excellent levels of enantioselectivity. Moreover, substrates bearing an a-ethyl group (5h) as well as primary benzylic substrates (5i) were also readily accommodated by our MPC thiocyanase lineage. Table .