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Iminoxyl radicals vs. tert-butylperoxyl radical in competitive oxidative C–O coupling with β-dicarbonyl compounds. Oxime ether formation prevails over Kharasch peroxidation

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Abstract

Oxidative coupling of oxime and β-dicarbonyl compounds dominates in a β-dicarbonyl compound/oxime/Cu(II)/t-BuOOH system; in the absence of oxime, oxidative coupling of t-BuOOH and a β-dicarbonyl compound (Kharasch peroxidation) takes place. The proposed conditions for oxidative coupling of oximes with dicarbonyl compounds require only catalytic amounts of copper salt and t-BuOOH serves as a terminal oxidant. The C–O coupling reaction proceeds via the formation of tert-butoxyl, tert-butylperoxyl and iminoxyl radicals. Apparently, tert-butylperoxyl radicals oxidize oxime into iminoxyl radical faster than they react with β-dicarbonyl compounds forming the Kharasch peroxidation product. Iminoxyl radicals are responsible for the formation of the target C–O coupling products; the yields are up to 77%.

Graphical abstract: Iminoxyl radicals vs. tert-butylperoxyl radical in competitive oxidative C–O coupling with β-dicarbonyl compounds. Oxime ether formation prevails over Kharasch peroxidation

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Publication details

The article was received on 22 Dec 2017, accepted on 30 Jan 2018 and first published on 05 Feb 2018


Article type: Paper
DOI: 10.1039/C7RA13587D
RSC Adv., 2018,8, 5670-5677
  • Open access: Creative Commons BY-NC license
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    Iminoxyl radicals vs. tert-butylperoxyl radical in competitive oxidative C–O coupling with β-dicarbonyl compounds. Oxime ether formation prevails over Kharasch peroxidation

    I. B. Krylov, S. A. Paveliev, N. S. Shumakova, M. A. Syroeshkin, B. N. Shelimov, G. I. Nikishin and A. O. Terent'ev, RSC Adv., 2018, 8, 5670
    DOI: 10.1039/C7RA13587D

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