THE ROLE OF ENTROPIC AND ELECTRONIC FACTORS IN CONTROLLING HOMO-1,4 ADDITION OF DIHALOCARBENES TO NORBORNADIENE-TYPE MOLECULES

Article abstract of DOI:10.1016/S0040-4039(00)77771-9

The proportion of 1,2 and homo-1,4 adducts obtained from the reaction of difluorocarbene with norbornadiene and its 7-oxa, 7-methyl, and 7,7-difluoro derivatives is reflected by the calculated energies of the frontier molecular orbitals of the dienes.It appears that the product composition is dictated by competing 1,2 electrophilic and homo-1,4 nucleophilic cheletropic reactions.