is pseudopericyclic if the primary changes in bonding occur within a cyclic array
of atoms at one (or more) of which nonbonding and bonding atomic orbitals interchange
roles. A formal example is the enol
enol prototropy of pentane-2,4-dione (acetylacetone).
Because the -
orbitals that interchange
roles are orthogonal, such a reaction does not proceed through a fully
and is thus not a pericyclic reaction
and therefore not governed by the rules that express orbital symmetry
restrictions applicable to pericyclic reactions.
PAC, 1994, 66, 1077
(Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994))
on page 1154
IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by
A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997).
XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic,
J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. https://doi.org/10.1351/goldbook