Abstract: Geometrically and optically pure (3R, 5E)-and (3RJZ)-1, 5-heptadien-3-ols undergo anionic oxy-Cope rearrangement under the exclusive control of oxyanion orientation with a 58-64% preference for equatorial oxygen. Six semicyclic dienols have also been synthesized where the preferred oxyanion-driven sigmatropic rearrangement pathway is obligatorily pitted against r-facial biases offered by 4-tert-butylcyclohexenyl, norbornenyl ...
