In these MD simulations, we restrained the forming N-C bond distance between the internal or terminal N of the Fe(III)-N3 and the benzylic carbon of radical 15 to simulate the NACs of the radical rebound with either the internal or terminal azide N atom. We performed 500 ns simulations with the (Re)-face of the benzylic radical exposed to the azide to mimic the radical rebound transition state leading to the major (R)-enantiomer of the azidation product. Our MD simulations revealed that the Ph group of the benzylic radical resides in between the nonheme Fe center and the H199 residue, which is trans to the E265 residue. The binding pocket cis to the E265 residue is blocked by Y255 and Y302 residues, which are connected by a hydrogen bond enabled by the F302Y mutation introduced during directed evolution. The O-H⋯π interaction between the Fe(III)-bound water and the Ph group on the radical was observed, although the O-H⋯π distance from the MD trajectories is longer than that in DFT-optimized structure, because the Ph group is also involved in π⋯π interaction with H153. This radical rebound geometry is consistent with the experimentally observed enantioinduction-when the (Re)-face of the benzylic radical is exposed to the azide, the smallest substituent H on the secondary benzylic radical is placed towards the relatively hindered L155F residue, whereas the (Si)-face radical addition is expected to be disfavored due to steric repulsions between the Me substituent on the benzylic carbon and L155F. This enantioinduction model is consistent with the experimentally observed increased enantioselectivity with the L155F and F302Y mutations.