The Separation of the Intramolecular Isotope Effect for the Cytochrome P-450 Catalyzed Hydroxylation of n-Octane into Its Primary and Secondary Components

Article abstract of DOI:10.1021/ja00241a040

The intramolecular isotope effect for the cytochrome P-450b ω-hydroxylation of <1,1,1-2H3>-n-octane was separated into its primary and secondary components by the method of Hanzlik (Hanzlik et al.J.Am.Chem.Soc. 1985, 107, 7164).The primary isotope effect was found to lie between 7.3 and 7.9 while the secondary isotope effect was found to lie between 1.09 and 1.14.These data are consistent with a highly symmetrical transition state with 15percent of the observed isotope effect being due to secondary isotope effects.Although the system was found to depart from the rule of the geometric mean, the phenomenon could not be attributed to tunneling.