Trinuclear Non‐Heme Iron Complexes Based on 4‐Substituted 2,6‐Diacylpyridine Ligands as Catalysts in Aerobic Allylic Oxidations

Rabe, V.; Frey, Wolfgang; Baro, Angelika

doi:10.1002/hlca.201100195

Cited by 5 publications

(3 citation statements)

References 49 publications

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“…Based on earlier work,183 trinuclear non‐heme Fe 3 (μ 3 ‐O) complexes 128 , 129 were prepared from diacylpyridine ligands 127 and Fe III salts (Scheme ) 184. 185…”

Section: Oxidation Of Activated Sp3 Ch Bonds With O2mentioning

confidence: 99%

Selective Catalytic Oxidation of CH Bonds with Molecular Oxygen

et al. 2012

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Although catalytic reductions, cross‐couplings, metathesis, and oxidation of CC double bonds are well established, the corresponding catalytic hydroxylations of CH bonds in alkanes, arenes, or benzylic (allylic) positions, particularly with O2, the cheapest, “greenest”, and most abundant oxidant, are severely lacking. Certainly, some promising examples in homogenous and heterogenous catalysis exist, as well as enzymes that can perform catalytic aerobic oxidations on various substrates, but these have never achieved an industrial‐scale, owing to a low space‐time‐yield and poor stability. This review illustrates recent advances in aerobic oxidation catalysis by discussing selected examples, and aims to stimulate further exciting work in this area. Theoretical work on catalyst precursors, resting states, and elementary steps, as well as model reactions complemented by spectroscopic studies provide detailed insight into the molecular mechanisms of oxidation catalyses and pave the way for preparative applications. However, O2 also poses a safety hazard, especially when used for large scale reactions, therefore sophisticated methodologies have been developed to minimize these risks and to allow convenient transfer onto industrial scale.

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“…Based on earlier work,183 trinuclear non‐heme Fe 3 (μ 3 ‐O) complexes 128 , 129 were prepared from diacylpyridine ligands 127 and Fe III salts (Scheme ) 184. 185…”

Section: Oxidation Of Activated Sp3 Ch Bonds With O2mentioning

confidence: 99%

Selective Catalytic Oxidation of CH Bonds with Molecular Oxygen

et al. 2012

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“…Iron is an obvious choice for the design of catalysts for C-H oxidations due to ample natural precedence in oxidases. [189][190][191][192] However, for allylic oxidations to enones, it has been difficult to create chemoselective iron-based catalysts. One of the first successful applications was the allylic oxidation of cholesteryl acetate by tris(acetylaceto-nato)iron(III) (0.1 equiv) with tert-butyl hydroperoxide (7.7 equiv) to give the enone 51 as main product (Scheme 31).…”

Section: Iron Reagentsmentioning

confidence: 99%

Allylic Oxidations of Olefins to Enones

Weidmann

Maison

2013

Synthesis

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Allylic oxidations of olefins to enones are C-H functionalizations and are valuable organic transformations that permit the synthesis of value-added products from simple precursors. A variety of stoichiometric and catalytic metal-based methods are available for these conversions. In addition, metal-free and biocatalytic protocols are gaining in importance. This review summarizes the available oxidation methods and compares their regio-and chemoselectivities.

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“…Amides of general structures 1 and 2 ( Figure 1 ) have a range of potential applications as ligands for catalysis, in molecular switches, and as metal binding agents. When combined with iron(II), ligands of this ilk can promote alkene dihydroxylation and allylic oxidation reactions akin to those mediated by non-heme iron oxidase enzymes (NHIOs) 1 2 3 4 5 6 7 8 9 ; in combination with cobalt(III) or iron(III), they may catalyse conversion of nitriles to primary amide products, as mimics of the metalloenzyme nitrile hydratase 10 11 12 13 .…”

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Synthesis and structural characterisation of amides from picolinic acid and pyridine-2,6-dicarboxylic acid

Devi

Barry

Houlihan

et al. 2015

Sci Rep

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Coupling picolinic acid (pyridine-2-carboxylic acid) and pyridine-2,6-dicarboxylic acid with N-alkylanilines affords a range of mono- and bis-amides in good to moderate yields. These amides are of interest for potential applications in catalysis, coordination chemistry and molecular devices. The reaction of picolinic acid with thionyl chloride to generate the acid chloride in situ leads not only to the N-alkyl-N-phenylpicolinamides as expected but also the corresponding 4-chloro-N-alkyl-N-phenylpicolinamides in the one pot. The two products are readily separated by column chromatography. Chlorinated products are not observed from the corresponding reactions of pyridine-2,6-dicarboxylic acid. X-Ray crystal structures for six of these compounds are described. These structures reveal a general preference for cis amide geometry in which the aromatic groups (N-phenyl and pyridyl) are cis to each other and the pyridine nitrogen anti to the carbonyl oxygen. Variable temperature 1H NMR experiments provide a window on amide bond isomerisation in solution.

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Trinuclear Non‐Heme Iron Complexes Based on 4‐Substituted 2,6‐Diacylpyridine Ligands as Catalysts in Aerobic Allylic Oxidations

Cited by 5 publications

References 49 publications

Selective Catalytic Oxidation of CH Bonds with Molecular Oxygen

Selective Catalytic Oxidation of CH Bonds with Molecular Oxygen

Allylic Oxidations of Olefins to Enones

Synthesis and structural characterisation of amides from picolinic acid and pyridine-2,6-dicarboxylic acid

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