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	Oxidation of Tertiary Amines by Cytochrome P450-Kinetic Isotope Effect as a Spin-State Reactivity Probe
	Li, Chunsen ; Wu, Wei ; Wu W(吴玮) ; Cho, Kyung-Bin（Hebrew Univ Jerusalem, Dept Organ Chem） ; Shaik, Sason（Hebrew Univ Jerusalem, Dept Organ Chem）
	2009-05
关键词	amine oxidation cytochrome P450 density functional calculations kinetic isotope effects spin selectivity
英文摘要	Two types of tertiary amine oxidation processes, namely, N-dealkylation and N-oxygenation, by compound I (Cpd I) of cytochrome P450 are studied theoretically using hybrid DFT calculations. All the calculations show that both N-dealkylation and N-oxygenation of trimethylamine (TMA) proceed preferentially from the low-spin (LS) state of Cpd I. Indeed, the computed kinetic isotope effects (KIEs) for the rate-controlling hydrogen abstraction step of dealkylation show that only the KIELS fits the experimental datum, whereas the corresponding value for the high-spin (HS) process is much higher. These results second those published before for N,N-dimethylaniline (DMA), and as such, they further confirm the conclusion drawn then that KIEs can be a sensitive probe of spin state reactivity. The ferric-carbinolamine of TMA decomposes most likely in a non-enzymatic reaction since the Fe-O bond dissociation energy (BDE) is negative. The computational results reveal that in the reverse reaction of N-oxygenation, the N-oxide of aromatic amine can serve as a better oxygen donor than that of aliphatic amine to generate Cpd I. This capability of the N-oxo derivatives of aromatic amines to transfer oxygen to the heme, and thereby generate Cpd I, is in good accord with experimental data previously reported.; Natural Science Foundation of China [20533020, 20873106]; The National Basic Research Program of China [2004CB719902]; DFG
语种	英语
出版者	WILEY-V C H VERLAG GMBH
内容类型	期刊论文
源URL	[http://dx.doi.org/doi:10.1002/chem.200802215]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Li, Chunsen,Wu, Wei,Wu W,et al. Oxidation of Tertiary Amines by Cytochrome P450-Kinetic Isotope Effect as a Spin-State Reactivity Probe[J],2009.
APA	Li, Chunsen,Wu, Wei,吴玮,Cho, Kyung-Bin,&Shaik, Sason.(2009).Oxidation of Tertiary Amines by Cytochrome P450-Kinetic Isotope Effect as a Spin-State Reactivity Probe..
MLA	Li, Chunsen,et al."Oxidation of Tertiary Amines by Cytochrome P450-Kinetic Isotope Effect as a Spin-State Reactivity Probe".(2009).

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