Green and Efficient: Iron-Catalyzed Selective Oxidation of Olefins to Carbonyls with O2

A mild and operationally simple iron-catalyzed protocol for the selective aerobic oxidation of aromatic olefins to carbonyl compounds is described. Catalyzed by a Fe­(III) species bearing a pyridine bisimidazoline ligand at 1 atm of O2, α- and β-substituted styrenes were cleaved to afford benzaldehy...

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Veröffentlicht in:Journal of the American Chemical Society 2015-07, Vol.137 (25), p.8206-8218
Hauptverfasser: Gonzalez-de-Castro, Angela, Xiao, Jianliang
Format: Artikel
Sprache:eng
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Zusammenfassung:A mild and operationally simple iron-catalyzed protocol for the selective aerobic oxidation of aromatic olefins to carbonyl compounds is described. Catalyzed by a Fe­(III) species bearing a pyridine bisimidazoline ligand at 1 atm of O2, α- and β-substituted styrenes were cleaved to afford benzaldehydes and aromatic ketones generally in high yields with excellent chemoselectivity and very good functional group tolerance, including those containing radical-sensitive groups. With α-halo-substituted styrenes, the oxidation took place with concomitant halide migration to afford α-halo acetophenones. Various observations have been made, pointing to a mechanism in which both molecular oxygen and the olefinic substrate coordinate to the iron center, leading to the formation of a dioxetane intermediate, which collapses to give the carbonyl product.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.5b03956