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| - An Orbital Phase Theory for the Torquoselectivity of theRing-Opening Reactions of 3-Substituted Cyclobutenes:Geminal Bond Participation
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| - We apply an orbital phase theory to the torquoselectivity of the electrocyclic reactions of3-substituted (X) cyclobutenes. The torquoselectivity is shown to be controlled by the orbital-phaserelation of the reacting πCC and σCC bonds with the σCX bond geminal to the σCC bond to be cleaved.The inward rotation of electron-donating σCX bonds and outward rotation of electron-withdrawingσCX bonds have been deduced from the orbital-phase theory. Enhancement of the inward rotationby the electron-donating capability of the σCX bonds is confirmed by the correlation between thetorquoselectivity and σCX orbital energy. The orbital overlaps between the geminal σCX (σCH) andσCC* bonds are found to be important as well. Unsaturated substituents with low-lying unoccupiedπ* orbitals also promote the inward rotation.
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