Citation: Shuang LI, Zi-Hao WEN, Min-Yi ZHANG. Theoretical Study of Iron Porphyrin Imine Specie of P411 Enzyme: Electronic Structure and Regioselectivity of C(sp³)-H Primary Amination[J]. Chinese Journal of Structural Chemistry, ;2021, 40(11): 1411-1422. doi: 10.14102/j.cnki.0254–5861.2011–3191 shu

Theoretical Study of Iron Porphyrin Imine Specie of P411 Enzyme: Electronic Structure and Regioselectivity of C(sp³)-H Primary Amination

Shuang LI ^{a, b} ,
Zi-Hao WEN ^b ,
Min-Yi ZHANG ^b,,

a.
College of Chemistry, Fuzhou University, Fuzhou 350108, China
b.
Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

Corresponding author: Min-Yi ZHANG, myzhang@fjirsm.ac.cn
Received Date: 24 March 2021
Accepted Date: 8 July 2021

Figures(14)

The cytochrome P411 enzyme is a variant of cytochrome P450_BM3 from Bacillus megaterium whose active site is an iron porphyrin imine ([Fe(Por)(NH)]^-) specie. This specie has been reported to successfully promote the primary amination of benzylic and allylic C(sp³)-H bonds. We employed density functional theory to study the electronic structure of the active site of P411 enzyme and the primary amination of C-H bond reaction that it catalyzes. The calculated spin densities and orbital values indicate the existence of resonance in this specie; namely, [(por)(–OH)Fe^Ⅳ–N^2-–H]^- ↔ [(por)(–OH)Fe^Ⅲ–N^•-–H]^-. The amination of C(sp³)-H bonds consists of two main reaction steps: hydrogen-atom abstraction and radical recombination, and the former is demonstrated to be the rate-determining step. Furthermore, we studied the regioselectivity of the amination of primary and secondary C(sp³)-H bonds. Our calculations indicated that the secondary C(sp³)-H bonds of the substrate would be more favored for the activation by P411 enzyme. These results provide valuable information for understanding the properties and selectivity of C-H/C-N bond-activation reactions catalyzed by the P411 enzyme or other similar enzymes.
- DFT,
- cytochrome P411 enzyme,
- C–H bond activation,
- enzyme catalysis
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Theoretical Study of Iron Porphyrin Imine Specie of P411 Enzyme: Electronic Structure and Regioselectivity of C(sp3)-H Primary Amination

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通讯作者: 陈斌, bchen63@163.com

Theoretical Study of Iron Porphyrin Imine Specie of P411 Enzyme: Electronic Structure and Regioselectivity of C(sp³)-H Primary Amination