Theoretical study of the electronic and steric effects in the inter and intramolecular radical additions

Abstract

The intramolecular addition of the ω-alkenyl radicals and the chain length influence in the cyclization process have been studied using MINDO/3 theoretical method. The partitioning of the total energy in local contributions is used to analyse the electronic and steric factors in the addition process. The free methyl radical additions to ethylene and propene have also been analysed and compared with the intramolecular additions. The comparison between the inter- and intramolecular additions shows that the first ones depend on the electronic structure of the olefin, while in the second, electronic and steric factors compete in the cycloaddition.