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1
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0342764516
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Wayne State University
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(a) Wayne State University.
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2
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0343634791
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Department of Pharmacology, University of Michigan
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(b) Department of Pharmacology, University of Michigan.
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3
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0342764515
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Department of Biological Chemistry, University of Michigan
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Department of Biological Chemistry, University of Michigan.
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4
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0003631066
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0342764513
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note
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Substrate 6 was previously studied with microsomes from livers of phenobarbital-treated rats, which contain mainly P450 2B1, and the purified 2B1 isozyme (ref 19). In that study, the alcohol products were converted to acetates that were analyzed, and the amounts of products 7-OAc and 8-OAc found were comparable. Given the apparent decomposition of alcohols 7 in GC analyses, the yields of 7 relative to 8 found here are in reasonable agreement with those previously reported.
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32
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36
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0018671537
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It is noteworthy that the concept of studying P450 hydroxylations with a probe that can differentiate between radicals and cations was put forth by Groves. Specifically, bicyclo[4.1.0]heptane was used as a probe because radicals and cations at the cyclopropylcarbinyl position of this species give different rearrangement products. P450-catalyzed hydroxylation of this probe, however, resulted in no rearrangement products. See: White, R. E.; Groves, J. T.; McClusky, G. A. Acta Biol. Med. Ger. 1979, 38, 475-489.
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note
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On the basis of the recalibration of PhSeH trapping kinetics (ref 30), the rate constant for rearrangement of the radical derived from probe 22 (ref 16) must be adjusted. This, in turn, results in an adjustment of the radical lifetime in the 2B1 oxidation of 22 (ref 10) from 70 to 100 fs.
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46
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0342764496
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note
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The lifetime of a transition state at ambient temperature from classical transition state theory is 170 fs.
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