COMPUTER-ASSISTED MECHANISTIC EVALUATION OF ORGANIC-REACTIONS .17. FREE-RADICAL CHAIN REACTIONS

A mechanistic model for free radical chain reactions has been developed for the computer program cameo. The controlling algorithm treats all reactions as a series of fundamental radical processes, i.e., abstractions, additions, and fragmentations. Chain-propagating steps are mimicked by automatic resubmission of selected intermediates. This paper provides an overview of radical chain processes and descriptions of the rules implemented for the logical prediction of chain reaction sequences. Several prominent examples that demonstrate the synthetic utility of free radical reactions and the success of the cameo program in predicting complex sequences are presented. An appendix which describes the algorithm for estimating homolytic bond dissociation energies is included. © 1990, American Chemical Society. All rights reserved.