Issue 58, 2025

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

Abstract

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 [FeV(O)–(NO2)bTAML] (2) as the reactive intermediate. The 3°:2° selectivity in hydrocarbons, kinetic isotope effect (KIE), and detailed kinetic studies indicate hydrogen atom abstraction (HAA) by [FeV(O)–(NO2)bTAML] (2) as the rate-determining step.

Graphical abstract: Halogenase-mimicking selective chlorination of unactivated C–H bonds by a Fe-complex

Supplementary files

Article information

Article type
Communication
Submitted
08 মে 2025
Accepted
06 জুন 2025
First published
11 জুন 2025
This article is Open Access
Creative Commons BY-NC license

Chem. Commun., 2025,61, 10827-10830

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

H. Kuiry, A. Gangopadhyay, B. Chandra and S. Sen Gupta, Chem. Commun., 2025, 61, 10827 DOI: 10.1039/D5CC02614H

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements