A general stereoselection rule governing the electrocyclic interactions has been proposed with a molecular orbital rationale. The reactions discussed from a unified point of view cover the ring-closure of polyenes, the Diels-Alder additions, 1,4-dipolar additions, the Cope and the Claisen rearrangements, the hydrogen and the proton migrations, 1,3-dipolar additions, the ring-opening of cyclic olefins, the deamination of cyclic unsaturated imines, 1,2-noncycloadditions, 1,2-eliminations, the nucleophilic displacement with allylic rearrangements, and other cyclic intermediate or complex formations. The relation to the molecular orbital symmetry has been also discussed.
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