Kinetics and Deuterium Kinetic Isotope Effects for the Thermal [1,7] Sigmatropic Rearrangements of Cis,cis-1,3,5-octatriene
Thermal isomerizations of cis,cis-1,3,5-octatriene at 60-111°C occur with activation parameters log A = 9.1 and Ea = 21.3 (to cis,cis,cis-2,4,6-octatriene) and Ea = 20.2 kcal mol-1 (to cis,cis,trans-2,4,6-octatriene). Primary deuterium kinetic isotope effects for these [1,7] sigmatropic shifts are found to be 6.4-7.7 and not markedly temperature dependent, indicative of a linear or nearly linear C7-H-C1 geometry in the transition-state structure.
J. E. Baldwin and P. Reddy, "Kinetics and Deuterium Kinetic Isotope Effects for the Thermal [1,7] Sigmatropic Rearrangements of Cis,cis-1,3,5-octatriene," Journal of the American Chemical Society, vol. 109, no. 26, pp. 8051-8056, American Chemical Society (ACS), Dec 1987.
The definitive version is available at http://dx.doi.org/10.1021/ja00260a017
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