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Energy Barriers to the Diels-Alder Cycloadditions and Cycloreversions of Cation-radicals in the Gas Phase

DOI: 10.1039/P29860001011

Source and publish data:

Journal of the Chemical Society. Perkin transactions II p. 1011 - 1014 (1986)

Update date:2022-09-26

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Authors:

Turecek, FrantisekTurecek, Frantisek

Havlas, ZdenekHavlas, Zdenek

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Article abstract of DOI:10.1039/P29860001011

The mechanism of the retro-Diels-Alder reaction of substituted bicyclo<2.2.1>hept-2-ene cation-radicals can be related to the energetics of the fragmentation.Concerted synchronous or asynchronous mechanisms are operative in reactions which occur at their thermochemical thresholds.The reverse process, the Diels-Alder reaction of a cation-radical with a molecule, has a negligible activation energy for symmetrical and slightly unsymmetrical systems, <(Z)-1,2-dihydroxyethene>+* + cyclopentadiene, +* + vinyl alcohol, <(E)-1-hydroxybuta-1,3-diene>+* + cyclopentadiene, and <(Z)-1-hydroxybuta-1,3-diene>+* + cyclopentadiene.The retro-Diels-Alder decomposition of the highly unsymmetrical 2-vinylbicyclo<2.2.1>hept-5-en-2-ol cation-radical proceeds in two steps and overcomes a barrier of 58-67 kJ mol-1 above the thermochemical threshold.The effect of bond-dissociation energies on the reaction mechanism is discussed.

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