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Dehydrogenative α-Oxygenation of Ethers with an Iron Catalyst

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Dehydrogenative α-Oxygenation of Ethers with an Iron Catalyst

Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, United Kingdom
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/ja502167h
Publication Date (Web): May 16, 2014
Copyright © 2014 American Chemical Society

Abstract

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Selective α-oxidation of ethers under aerobic conditions is a long-pursued transformation; however, a green and efficient catalytic version of this reaction remains challenging. Herein, we report a new family of iron catalysts capable of promoting chemoselective α-oxidation of a range of ethers with excellent mass balance and high turnover numbers under 1 atm of O2with no need for any additives. Unlike metalloenzymes and related biomimetics, the catalyst produces H2 as the only byproduct. Mechanistic investigations provide evidence for an unexpected two-step reaction pathway, which involves dehydrogenative incorporation of O2into the ether to give a peroxobisether intermediate followed by cleavage of the peroxy bond to form two ester molecules, releasing stoichiometric H2 gas in each step. The operational simplicity and environmental friendliness of this methodology affords a useful alternative for performing oxidation, while the unique ability of the catalyst in oxygenating a substrate via dehydrogenation points to a new direction for understanding metalloenzymes and designing new biomimetic catalysts.
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