Figure 7. Reaction intermediate binding modes.

Iminium reaction intermediates were docked in the TfNCS active site using AutoDock Vina⁴². The structure of the docked iminium ligand is shown above a depiction of the mechanistically relevant binding modes. The side chains of mechanistically important amino acids or amino acids modified in this study are shown as sticks. (a) Intermediate derived from 4-HPAA, the natural aldehyde substrate. (b) Intermediate derived from 4-phenylcyclohexanone 9, a representative example of the docking results of cyclohexanone-derived compounds. (c) Intermediate derived from phenylacetone 4 with trans (E) double bond. (d) Intermediate derived from phenylacetone 4 with cis (Z) double bond. Complete docking results can be found in Supplementary Figs 7 and 8 and Supplementary Table 1.