Mechanism of 1,2-shift through p -complex transition state

A systematic calculation of the potential curves or surfaces for 1,2-shift has been realized by using MNDO or other models in MOPAC programs. By referring to the previous authors' viewpoints, the 1,2-shift can be divided into two categories. 1,2-electron-deficient shift is that the electronic configuration of the atom which accepts the migrating group is a cation or an electron- deficient atom, and 1,2-anion shift is the one that the accepted atom of the migration group is a negative ion. In terms of the experimental facts and the calculation of the potential surfaces, in electron-deficient shift such as Beckmann or Baeyer-Villiger rearrangement, the migration occurs through a transition complex formed between the p -bond and the cation or electron-deficient migrating group, but in anion shift such as Wittig or Stevens rearrangement, the electron pair in p -orbit excites at first to p * orbit, and then the migration occurs through the new formed complex between the anion migration group and the vacant p orbit. The above mechanisms explain reasonably the intramolecular properties, the configuration retentions of the migration group, and the corresponding migratory aptitudes of the two type 1,2-shifts. The partial and less important free radical reaction of 1,2-anion shift has been explained by the p -complex mechanism too.