Green and Efficient: Iron-Catalyzed Selective Oxidation of Olefins to Carbonyls with O-2

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 O-2, alpha- and beta-substituted styrenes were cleaved to afford ben...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 137; no. 25; pp. 8206 - 8218
Main Authors Gonzalez-de-Castro, Angela, Xiao, Jianliang
Format Journal Article
LanguageEnglish
Published WASHINGTON Amer Chemical Soc 01.07.2015
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
LOW-TEMPERATURE PHOTOOXYGENATION
ASYMMETRIC TRANSFER HYDROGENATION
SINGLET OXYGEN REACTIONS
CIS-DIHYDROXYLATION
STYRENE
CLEAVAGE
FUNCTIONAL-MODEL
DOUBLE-BOND
MOLECULAR-OXYGEN
C-H
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Summary: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 O-2, alpha- and beta-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 alpha-halo-substituted styrenes, the oxidation took place with concomitant halide migration to afford alpha-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.
Bibliography:researchfish
UKRI
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.5b03956