Energetics for the Oxygen Rebound Mechanism of Alkane Hydroxylation by the Iron-Oxo Species of Cytochrome P450
Energetics for the Oxygen Rebound Mechanism of Alkane Hydroxylation by the Iron-Oxo Species of Cytochrome P450
复制标题
细胞色素 P450 的铁氧化物种对烷烃羟基化的氧反弹机制的能量学
DOI：
10.1246/bcsj.73.2669
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发表时间：
2000
影响因子：
4
通讯作者：
Yoshihisa Kagawa
中科院分区：
文献类型：
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作者：
K. Yoshizawa;Y. Shiota;Yoshihisa Kagawa
讨论了用细胞色素P450的化合物I模型对烷烃羟基化反应途径的密度泛函理论计算结果。我们的计算表明，乙烷的H原子抽象的过渡态涉及线性（Fe）O…H…C阵列，并且生成的碳自由基与铁羟基结合。这一计算结果在一定程度上与氧反弹机制相一致，即氢原子被铁氧直接抽离发生在反应途径的初始阶段。然而，从能量图来看，羟基铁不能被看作是稳定的反应中间体。我们的结果可能与通常假设和典型的氧反弹机制的自由基物种具有有限寿命和羟基从铁中心位移的障碍的模型不一致。
Density-functional-theory calculational results on the reaction pathway for alkane hydroxylation by a compound I model of cytochrome P450 are discussed. Our calculations demonstrate that the transition state for the H-atom abstraction of ethane involves a linear (Fe)O…H…C array and that the resultant carbon radical is bound to the iron-hydroxo species. This comptational result is partly consistent with the oxygen rebound mechanism in that the direct H-atom abstraction by the iron-oxo species takes place in the initial stages of the reaction pathway. However, the iron-hydroxo species cannot be viewed as a stable reaction intermediate in view of the energy diagram. Our results may not be consistent with the model of a free radical species with a finite lifetime and barrier to displacement of the OH group from the iron center that is commonly assumed and typically stated for the oxygen rebound mechanism.
铁 (III) 和铬 (III) 催化的去质子化 C-H 活化
DOI：
--
发表时间：
2021
期刊：
影响因子：
--
作者：
瀬尾 珠恵;豊島 直喜;久保田 浩司;伊藤 肇;Rui Shang and Eiichi Nakamura
通讯作者：
Rui Shang and Eiichi Nakamura
可溶性甲烷单加氧酶对甲烷羟基化机理的DFT研究
DOI：
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发表时间：
2011
期刊：
影响因子：
--
作者：
Huang;S.-P.;Xu;H.;Bello;I.;Zhang;R.Q.;Huang Shu-Ping;Huang Shu-Ping;Huang Shu-Ping
通讯作者：
Huang Shu-Ping