模拟卤素酶的铁络合物对未活化C-H键的选择性氯化反应

IF 4.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemical Communications Pub Date : 2025-06-11 DOI:10.1039/d5cc02614h

Himangshu Kuiry , Anish Gangopadhyay , Bittu Chandra , Sayam Sen Gupta

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引用次数: 0

摘要

在本研究中，我们报道了以次氯酸钠为氯源，Fe-bTAML （bTAML：双缩脲修饰的四氨基大环配体）介导的选择性脂肪族C-H键氯化反应。在乙腈-水介质中，通过各种未活化的C-H键，主要产生氯化产物而不是羟基化产物。内甲烷中重排氯化产物的形成和顺式二甲基环己烷中立体保留的缺失表明了长寿命的笼状逃逸碳自由基中间体的参与。紫外可见光谱和EPR光谱分析证实了[FeV(O)-(NO2)bTAML]-(2)作为反应中间体的存在。碳氢化合物的3°：2°选择性、动力学同位素效应（KIE）和产物形成剖面表明，[FeV(O)-(NO2)bTAML]-(2)的氢原子萃取（HAA）是决定速率的步骤。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Halogenase-mimicking selective chlorination of unactivated C–H bonds by a Fe-complex†

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Halogenase-mimicking selective chlorination of unactivated C–H bonds by a Fe-complex†

In this study, we report a selective aliphatic C–H bond chlorination mediated by Fe-bTAML (bTAML: biuret-modified tetraamido macrocyclic ligand) using sodium hypochlorite as the chlorine source. The reaction predominantly yields chlorinated products over hydroxylated ones across various unactivated C–H bonds in acetonitrile–water medium. The formation of rearranged chlorinated products in norcarane and the absence of stereo-retention in cis-dimethylcyclohexane suggests the involvement of a long-lived, cage-escaped carbon radical intermediate. UV-Vis and EPR spectroscopic analyses confirm the presence of [Fe^V(O)–(NO₂)bTAML]⁻ () as the reactive intermediate. The 3°:2° selectivity in hydrocarbons, kinetic isotope effect (KIE), and detailed kinetic studies indicate hydrogen atom abstraction (HAA) by [Fe^V(O)–(NO₂)bTAML]⁻ () as the rate-determining step.

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来源期刊

Chemical Communications 化学-化学综合

CiteScore

8.60

自引率

4.10%

发文量

2705

审稿时长

1.4 months

期刊介绍： ChemComm (Chemical Communications) is renowned as the fastest publisher of articles providing information on new avenues of research, drawn from all the world''s major areas of chemical research.