Based on these results, we elected to evaluate the influence of N-arylsulfonyl allylaniline with various substituents at the ortho position of the migrating aryl group by a density-functional theory (DFT) computational study at the SMD(C6H6) ωB97XD/Def2TZVPP//ωB97XD/Def2SVP level of theory (see further computational details in the supporting information), including quasi-harmonic corrections with the Goodvibes program. For all three substrates, 1a, 1b and 1c, we observed that formation of the first transition state was the rate-determining step for all possible reaction pathways (Scheme 2B, see the complete free energy profiles in the supporting information). For substrate 1a, the least stable and highest energy transition state occurs for ipso addition at the arene attached to sulfur (15.3 kcal/mol), while the most stable transition state arises from ortho addition at the same aromatic group (14.6 kcal/mol). The transition state energy for attack at the aromatic ring bonded directly to N has an energy of 15.2 kcal/mol. By analysing the energies of these three transition states, the predicted radio of the products is calculated to be: 2a: 2a': 2a'' = 17: 61: 22 (Scheme 2B).