ELECTRONIC CONTROL OF THE STEREOCHEMISTRY OF ELECTROPHILIC AND NUCLEOPHILIC-ATTACK ON DOUBLE-BONDS IN 6-MEMBERED RINGS

CNDO and ab initio MO calculations reveal a deformation of the π* and π orbitals of cyclohexene in the axial directions, thus providing a reasonable explanation for the axial attack on cyclohexene either by electrophiles or by nucleophiles. It is shown in the case of 1-butene by an ab initio calculation that this orbital deformation is a result of the mixing of the π and σ orbitals of the double bond under the influence of the allylic C-C bond. © 1979.