Predicting regioselectivity in nucleophilic aromatic substitution.

摘要: We have investigated practical and computationally efficient methods for the quantitative prediction of regioisomer distribution in kinetically controlled nucleophilic aromatic substitution reactions. One is based on calculating relative stabilities isomeric σ-complex intermediates using DFT. show that predictions from this method can be used quantitatively both anionic nucleophiles with F– as leaving group, well neutral HF group. The approach failed when group was Cl/HCl or Br/HBr, nucleophiles, because difficulties finding relevant structures. An where we assumed a concerted step such transition state structures gave useful results. Our results are consistent other theoretical works, stable has been identified some cases, whereas others indicated to proceed via ...