Issue 33, 2010
From the journal:

Physical Chemistry Chemical Physics

Quantum chemical investigation of the thermal rearrangement of cis- and trans-pinane†

Daniel Kinzel,a   Achim Stolle,b   Bernd Ondruschkab  and  Leticia González*a  

* Corresponding authors

a Institute for Physical Chemistry, Friedrich-Schiller University Jena, Helmholtzweg 4, D-07743 Jena, Germany
E-mail: leticia.gonzalez@uni-jena.de

b Institute for Technical Chemistry and Environmental Chemistry, Friedrich-Schiller University Jena, Lessingstraße 12, D-07743 Jena, Germany
E-mail: Achim.Stolle@uni-jena.de

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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Article information

DOI
https://doi.org/10.1039/C001019G
Article type
Paper
Submitted
15 Jan 2010
Accepted
04 May 2010
First published
08 Jun 2010

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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