Computational Mechanistic Investigations of Biocatalytic Nitrenoid C−H Functionalizations via Engineered Heme Proteins
Computational Mechanistic Investigations of Biocatalytic Nitrenoid C−H Functionalizations via Engineered Heme Proteins
复制标题
通过工程血红素蛋白生物催化类氮化合物 C–H 功能化的计算机制研究
DOI：
10.1002/cbic.202300260
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发表时间：
2023
期刊：
影响因子：
3.2
通讯作者：
Chu, Jia‐Min
中科院分区：
文献类型：
--
作者：
Zhang, Yong;Chu, Jia‐Min
工程血红素蛋白被开发为具有许多优异的生物催化类氮C-H官能化。计算方法，如密度泛函理论（DFT），混合量子力学/分子力学（QM/MM），和分子动力学（MD）的计算，以帮助了解这些血红素氮烯转移反应的一些重要的机理方面。本文综述了生物催化分子内和分子间C-H胺化/酰胺化反应途径的计算结果，重点介绍了反应性、区域选择性、对映体选择性、非对映体选择性以及底物取代基、轴向配体、金属中心和蛋白质环境的影响。对这些反应的一些重要的共性和独特的机理特征进行了描述，并对今后的发展作了简要的展望。
Engineered heme proteins were developed to possess numerous excellent biocatalytic nitrenoid C−H functionalizations. Computational approaches such as density functional theory (DFT), hybrid quantum mechanics/molecular mechanics (QM/MM), and molecular dynamics (MD) calculations were employed to help understand some important mechanistic aspects of these heme nitrene transfer reactions. This review summarizes advances of computational reaction pathway results of these biocatalytic intramolecular and intermolecular C−H aminations/amidations, focusing on mechanistic origins of reactivity, regioselectivity, enantioselectivity, diastereoselectivity as well as effects of substrate substituent, axial ligand, metal center, and protein environment. Some important common and distinctive mechanistic features of these reactions were also described with brief outlook of future development.