COMPUTER-ASSISTED MECHANISTIC EVALUATION OF PERICYCLIC REACTIONS
Abstract
CAMEO, an interactive computer program that assists in the mechanistic evaluation of organic reactions, is under continued development. It has been significantly expanded by the addition of a module for thermal pericyclic chemistry. Sophisticated predictions of the likelihood and regioselectivity of cycloadditions involving up to 10 (pi) electrons are now possible. The heuristics were based on the frontier molecular orbital method. Consequently, it was necessary to devise efficient algorithms for the prediction of the energies and relative coefficients of frontier molecular orbitals. Sigmatropic processes, including the {2,3} and the {3,3} rearrangements as well as hydrogen and carbon migrations, have also been implemented. In addition, the necessary heuristics for and the incorporation of electrocyclic reactions, cheletropic extrusions, and the reverse Diels-Alder reactions are described. Finally, a general scheme for the treatment of periselectivity is presented.
Degree
Ph.D.
Subject Area
Organic chemistry
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