Issue 77, 2015

Mechanistic elucidation of C–H oxidation by electron rich non-heme iron(iv)–oxo at room temperature

Abstract

Non-heme iron(IV)–oxo species form iron(III) intermediates during hydrogen atom abstraction (HAA) from the C–H bond. While synthesizing a room temperature stable, electron rich, non-heme iron(IV)–oxo compound, we obtained iron(III)–hydroxide, iron(III)–alkoxide and hydroxylated-substrate-bound iron(II) as the detectable intermediates. The present study revealed that a radical rebound pathway was operative for benzylic C–H oxidation of ethylbenzene and cumene. A dissociative pathway for cyclohexane oxidation was established based on UV-vis and radical trap experiments. Interestingly, experimental evidence including O-18 labeling and mechanistic study suggested an electron transfer mechanism to be operative during C–H oxidation of alcohols (e.g. benzyl alcohol and cyclobutanol). The present report, therefore, unveils non-heme iron(IV)–oxo promoted substrate-dependent C–H oxidation pathways which are of synthetic as well as biological significance.

Graphical abstract: Mechanistic elucidation of C–H oxidation by electron rich non-heme iron(iv)–oxo at room temperature

Supplementary files

Article information

Article type
Communication
Submitted
10 Jun 2015
Accepted
03 Aug 2015
First published
04 Aug 2015
This article is Open Access
Creative Commons BY-NC license

Chem. Commun., 2015,51, 14469-14472

Author version available

Mechanistic elucidation of C–H oxidation by electron rich non-heme iron(IV)–oxo at room temperature

S. Rana, A. Dey and D. Maiti, Chem. Commun., 2015, 51, 14469 DOI: 10.1039/C5CC04803F

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