Criteria for pericyclic and pseudopericyclic character of electrocyclization of (Z)-1,2,4,6-heptatetraene and (2Z)-2,4,5-hexatriene-1-imine |
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Authors: | Shogo Sakai |
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Affiliation: | (1) Department of Chemistry, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan |
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Abstract: | The electrocyclic reaction mechanisms of (Z)-1,2,4,6-heptatetraene and (2Z)-2,4,5-hexatriene-1-imine were studied by ab initio MO methods. The activation energy barrier height of the electrocyclic reaction of (Z)-1,2,4,6-heptatetraene is extremely a low energy barrier of 8.58 kcal/mol by a MRMP method. The activation energy barrier height of the electrocyclic ring closure of the trans-type of (2Z)-2,4,5-hexatriene-1-imine is lower by 3.18 kcal/mol than that of (Z)-1,2,4,6-heptatetraene. These low energy barriers come from some orbital interactions relating to allene group. For the reaction of (Z)-1,2,4,6-heptatetraene, the interactions of the vertical and side π orbitals of the allene group with another terminal π orbital are important at the transition state. The interaction of the vertical π orbital of allene group with a lone pair orbital of N atom is dominant at the transition state of the reaction of the trans-type of (2Z)-2,4,5- hexatriene-1-imine. The electrocyclic mechanism of the cis-type of (2Z)-2,4,5-hexatriene-1-imine was also discussed. Contribution of the Mark S. Gordon 65th Birthday Festschrift issue. |
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