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首页> 外文期刊>Chemistry: A European journal >Oxidation of Tertiary Amines by Cytochrome P450—Kinetic Isotope Effect as a Spin-State Reactivity Probe
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Oxidation of Tertiary Amines by Cytochrome P450—Kinetic Isotope Effect as a Spin-State Reactivity Probe

机译：细胞色素P450氧化叔胺-运动同位素效应作为自旋态反应探针

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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 Noxygenation of trimethylamine (TMA) proceed preferentially from the lowspin (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,Ndimethylaniline (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.
机译：理论上，使用混合DFT计算研究了两种类型的叔胺氧化过程，即通过细胞色素P450的化合物I（Cpd I）进行的N-脱烷基化和N-加氧。所有计算结果均表明，三甲胺（TMA）的N-脱烷基化和Noxygenation均优先从Cpd I的低旋（LS）状态进行。实际上，脱烷基化速率控制的氢提取步骤的动力学同位素效应（KIEs）显示认为只有KIELS拟合实验数据，而高旋转（HS）过程的相应值要高得多。这些结果仅次于之前发表的有关N，N二甲基苯胺（DMA）的结果，因此，它们进一步证实了得出的结论，即KIEs可以作为自旋态反应性的灵敏探针。由于Fe-O键的离解能（BDE）为负，因此TMA的铁-卡宾醇胺最有可能在非酶反应中分解。计算结果表明，在N加氧的逆反应中，芳族胺的N-氧化物可以比脂肪族胺产生更好的氧供体，从而生成CpdI。芳族胺的N-氧代衍生物具有这样的能力将氧转移到血红素上，从而生成Cpd I，与先前报道的实验数据非常吻合。

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