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Issue 33, 2010
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Quantum chemical investigation of the thermal rearrangement of cis- and trans-pinane

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Abstract

The thermal rearrangement reactions of cis-pinane, 1, and trans-pinane, 2, into β-citronellene, 3, and isocitronellene, 4, have been investigated using ab initio multiconfigurational CASSCF and CASSCF MP2 calculations. Concerted as well as stepwise retro-[2+2]-cycloaddition conversion mechanisms are discussed and the corresponding stationary points along the relevant reaction paths from the bicyclic starting compounds into their acyclic isomers have been optimized. Our calculations show that the stepwise retro-[2+2]-cycloaddition via biradicals is energetically favoured with respect to the concerted mechanism. In the biradical pathways to 3 and 4, it was found that a gauche ring opening of the cyclobutane ring in 1 and 2, respectively, shows significantly lower activation barriers than the competing anti ring opening. With the predicted reaction paths, the calculated activation energies are in very good agreement with experimental values. The reaction mechanisms can explain the differences in the reactivity of 1 and 2, as well as the selectivity differences with respect to the formation of 3 and 4, reported in previous kinetic studies.

Graphical abstract: Quantum chemical investigation of the thermal rearrangement of cis- and trans-pinane

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Publication details

The article was received on 15 Jan 2010, accepted on 04 May 2010 and first published on 08 Jun 2010


Article type: Paper
DOI: 10.1039/C001019G
Citation: Phys. Chem. Chem. Phys., 2010,12, 9884-9892
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    Quantum chemical investigation of the thermal rearrangement of cis- and trans-pinane

    D. Kinzel, A. Stolle, B. Ondruschka and L. González, Phys. Chem. Chem. Phys., 2010, 12, 9884
    DOI: 10.1039/C001019G

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