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Green and Efficient: Iron-Catalyzed Selective Oxidation of Olefins to Carbonyls with O2
journal contribution
posted on 2015-07-01, 00:00 authored by Angela Gonzalez-de-Castro, Jianliang XiaoA 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.
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EfficientformationchemoselectivityOlefinspeciespyridine bisimidazoline ligandolefinsOxidationCatalyzedmechanismFeiron center1 atmbenzaldehydecarbonyl productoxidationVarious observationsolefinic substratecarbonyl compoundshalohalide migrationgroup toleranceCarbonylyieldketoneacetophenonestyreneO 2Adioxetane
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