Primary Deuterium Kinetic Isotope Effects for the Thermal [1,7] Sigmatropic Rearrangement of 7-methylocta-1,3(Z),5(Z)-triene
7-Methylocta-1,3(Z),5(Z)-triene isomerizes to 2-methylocta-2,4(Z),6(Z)-triene over the temperature range 60-115 °C through a first-order process characterized kinetically by the activation parameters log AH = 9.8 and EaH = 21.5 kcal/mol. Parallel kinetic work with the 7-deuterio-7-methyloctatriene establishes the Arrhenius parameters log AD = 10.3 and EaD = 23.5 kcal/mol. Thus AD/AH = 3.2 and (EaD - EaH) = 2.0 kcal/mol, and a substantial tunneling component for the [1,7] sigmatropic hydrogen migration is evident.
J. E. Baldwin and P. Reddy, "Primary Deuterium Kinetic Isotope Effects for the Thermal [1,7] Sigmatropic Rearrangement of 7-methylocta-1,3(Z),5(Z)-triene," Journal of the American Chemical Society, vol. 110, no. 24, pp. 8223 - 8228, American Chemical Society (ACS), Nov 1988.
The definitive version is available at https://doi.org/10.1021/ja00232a040
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© 1988 American Chemical Society (ACS), All rights reserved.
01 Nov 1988