Journal of the Chemical Society Perkin Transactions 2 · 1998 · 21 citations · 20 references
Natural SciencesChemistryPhysicsComputational ChemistryOrganic ChemistryPhysical ChemistryAb Initio MethodsElectron CorrelationHeterocyclic ChemistryMolecular Orbital TheoryAb Initio CalculationsAb Initio Molecular CalculationsConjugated DienesHeterocyclic ReactivityTransition State StructureTransition-state Analysis Of Cycloadditionπ Interactions
The dimerisation and competitive cycloaddition of 2-methoxycarbonylbuta-1,3-diene with electron-rich dienes has been investigated. Experimental results provide evidence that the enthalpy of the π-system significantly influences the energy of the transition state of cycloadditions of this type. This has been corroborated by ab initio calculations. We propose an early reorganisation of the π-electrons in such cycloadditions to explain the influence stated above.
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