期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 69, 期 21, 页码 7246-7249出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo049081y
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We apply an orbital phase theory to the torquoselectivity of the electrocyclic reactions of 3-substituted (X) cyclobutenes. The torquoselectivity is shown to be controlled by the orbital-phase relation of the reacting pi(CC) and sigma(CC) bonds with the sigma(CX) bonds geminal to the sigma(CC) bond to be cleaved. The inward rotation of electron-donating sigma(CX) bonds and outward rotation of electron-withdrawing sigma(CX) bonds have been deduced from the orbital-phase theory. Enhancement of the inward rotation by the electron-donating capability of the sigma(CX) bonds is confirmed by the correlation between the torquoselectivity and sigma(CX) orbital energy. The orbital overlaps between the geminal sigma(CX) (sigma(CH)) and sigma(CC)* bonds are found to be important as well. Unsaturated substituents with low-lying unoccupied pi* orbitals also promote the inward rotation.
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