Intramolecular determination of primary kinetic isotope effects in hydroxylations catalyzed by cytochrome P-450 |
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Authors: | Leonard M Hjelmeland Lewis Aronow James R Trudell |
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Institution: | Departments of Pharmacology and Anesthesia Stanford University, Stanford, California 94305 USA |
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Abstract: | Isotope effects for hydroxylation reactions catalyzed by cytochrome P-450 have usually been measured by comparing the overall reaction velocities of deuterated and nondeuterated substrates. Since the rate-limiting step is probably not the single reaction involving covalent bond cleavage, such an approach does not yield information about the primary isotope effect. We measured the primary kinetic isotope effect for benzylic hydroxylation by a method utilizing intramolecular competition, using the symmetrical substrate 1,3-diphenylpropane-1,1-d2. These experiments yield a value of , a larger effect than has previously been reported for benzylic hydroxylations. |
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Keywords: | To whom requests for reprints should be addressed Recipient of an Upjohn predoctoral fellowship |
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