Computer-assisted mechanistic evaluation of free radical reactions
Abstract
CAMEO is an interactive program that predicts the products of organic reactions given starting materials and conditions. The program has been extended to include a mechanistic model for free radical reactions. The operational premise treats all reactions as a series of fundamental radical processes; i.e., abstractions, additions, and fragmentations are explicitly enacted. Chain propagating steps are mimicked by automatic resubmission of selected intermediates. This thesis provides an overview of radical chain processes and descriptions of the rules implemented for the logical prediction of chain reaction sequences. Refinements to encompass diradical processes i.e., thermal unimolecular rearrangements and related reactions, are also discussed. Diradicals require some special treatment, as interactions between the unpaired electrons become important and recombination and disproportionation steps are major competitors with radical propagation. The biradical rearrangement steps have, however, been well integrated with the existing propagation algorithm. 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.
Degree
Ph.D.
Advisors
Jorgensen, Purdue University.
Subject Area
Organic chemistry
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