Fig. 2.

Calculated catalytic cycle and energetics of AsqJ. a The first part of the reaction cycle, comprising oxygen activation, decarboxylation of αKG, and two subsequent PCET reaction steps. b The second part of the reaction involving epoxidation of the substrate. All energies refer to free energies calculated in the quintet state at B3LYP-D3/def2-TZVP/ε = 4 level of theory with vibrational and entropic corrections at the B3LYP-D3/def2-SV(P)/ε = 4 level. Barriers are obtained from reaction pathway optimizations (Methods). See also Supplementary Movies 1 and 2, and Supplementary Figs. 3 and 9 for the optimized intermediate structures. Free energy profiles along the triplet surface are shown in Supplementary Figs. 6 and 7