A Theoretical Study on Chapman Rearrangement

Abstract Some Chapman rearrangements are investigated using HF and B3LYP methods combined with two different basis sets (6‐31G** and 6‐31++G**) and both finite difference model and Janak's approximation. It is shown that although minimum polarizability (MPP) and maximum hardness (MHP) principles are always valid in these reactions, minimum electrophilicity principle (MEP) is followed just when DFT method (B3LYP) is used. The Morrel's rules are also successfully applied in predicting the validity of MEP in these rearrangements. Therefore, it seems that in the study of this kind of reaction, the results of DFT are more reliable than those of HF.