cis-Dihydroxylation of electron deficient olefins catalysed by an oxo-bridged diiron(III) complex with H2O2

Kejriwal, Ambica; Biswas, Sachidulal; Biswas, Achintesh Narayan; Bandyopadhyay, Pinaki

doi:10.1016/j.molcata.2015.11.023

Cited by 8 publications

(6 citation statements)

References 45 publications

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“…Thus, we substantiated the next mechanism of xylenol orange N-oxidation: The chelates of different organic ligands L with ferric iron ions was shown to be the catalysts of organic substrates X oxyfunctionalization by H2O2 [23][24][25][26] The oxidation of ferric xylenol orange chelates by hydrogen peroxide is oxyfunctionalization reaction and not free radical chain destruction. The proposed mechanism includes steps such as N-oxidation, Cope elimination, and certain rearrangements with possible products oligomerization.…”

Section: Discussionmentioning

confidence: 57%

Oxidation of Ferric Xylenol Orange Chelates by Hydrogen Peroxide in Aqueous Solution: Conception of Oxygen Singlet Atoms Generation From Hydrogen Peroxide

Chumakov

Kotelnikov

Slizhov

2018

IVUZKKT

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We observed for the first time the reaction of oxidation of ferric xylenol orange chelates by hydrogen peroxide in aqueous solution. The reaction is accompanied with decoloration of the violet aqueous solution. Based on generally accepted conception, there is a process of free radical chain oxidation of indicator molecule in the solution. However, after investigating the final colorless solution by 1H NMR-spectroscopy we found the modified but not broken structure in which the initial hydrocarbon core remained mainly unchanged. We concluded that kind of reaction was an oxyfunctionalization by hydrogen peroxide versus free radical chain destruction. We argued steps of the reaction such as N-oxidation, Cope’s elimination, and certain rearrangements with possible products oligomerization. There was a need to explain the mechanism of interaction between the ferric iron ion and the hydrogen peroxide molecule and to argue the nature of intermediate reactive oxygen species. There is similarity between the ferric-catalyzed hydroperoxide xylenol orange oxidation and the peroxygenase-catalyzed biochemical oxyfunctionalization reactions. However, based on literature data and molecular orbital modeling, we proposed another mechanism of interaction between the ferric iron ion and the hydrogen peroxide molecule instead the tetravalent iron generation. Concretely, we proposed the hydrogen peroxide zwitter-ionization (isomerization to oxywater molecule) and subsequent intramolecular disproportionation with generation of a water molecule and a singlet oxygen atom as a reactive oxygen species. In this view, the iron ion oxidation state is unchanged during the reaction and remains ferric. An oxyfunctionalization of any organic substrate by hydrogen peroxide in the presence of ferric iron ions is promising approach in organic synthesis. However, the usage of organic ligands for ferric iron ions as components of catalysts is limited and requires only non-oxidizable compounds. On the other hand, one can choose an oxidation substrate as a ligand for ferric iron ions that is the formation of chelate complex of ferric catalyst with an organic substrate.Forcitation:Chumakov A.A., Kotelnikov O.A., Slizhov Yu.G. Oxidation of ferric xylenol orange chelates by hydrogen peroxide in aqueous solution: conception of oxygen singlet atoms generation from hydrogen peroxide. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 2. P. 15-22

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Section: Discussionmentioning

confidence: 57%

Oxidation of Ferric Xylenol Orange Chelates by Hydrogen Peroxide in Aqueous Solution: Conception of Oxygen Singlet Atoms Generation From Hydrogen Peroxide

Chumakov

Kotelnikov

Slizhov

2018

IVUZKKT

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“…μ-Oxodiiron complexes are known to play a role in oxygen atom transfer reactions, but their role in C–C coupling reactions has not been established. − The complexes [FeL1(Cl 2 )] + , [FeL4(Cl 2 )] + , and [FeL5(Cl) 2 ] + were explored due to the well-documented facile formation of μ-oxodiiron complexes in solutions with a pH above 1. − [FeL4(Cl 2 )] + and [FeL5(Cl) 2 ] + (Figure ) were added to the series to explore the impact of steric bulk on the N-atoms because it was hypothesized that the steric bulk in ligands L4 and L5 would impact the formation or stability of the μ-oxodiiron complexes. In the presence of Et 3 N and H 2 O, [FeL1(Cl 2 )] + and [FeL4(Cl 2 )] + readily formed μ-oxodiiron complexes 1 and 2 (Scheme ), respectively.…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Insights into Iron-Catalyzed C–H Bond Activation and C–C Coupling

et al. 2021

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Iron-catalyzed C−C coupling reactions of pyrrole provide a unique alternative to the traditional Pd-catalyzed counterpart. However, many details regarding the actual mechanism remain unknown. A series of macrocyclic iron(III) complexes were used to evaluate specifics related to the role of O 2 , radicals, and μ-oxodiiron-complex participation in the catalytic cycle. It was determined that the mononuclear tetra-azamacrocyclic complex is a true catalyst and not a stoichiometric reagent, while more than one equivalent of a sacrificial oxidant is needed. Furthermore, the reaction does not proceed through an organic radical pathway. μ-Oxodiiron complexes are not involved in the main catalytic pathway, and the dimers are, in fact, off-cycle species that decrease catalytic efficiency.

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“…Iron catalyzed syn -dihydroxylation constitutes an interesting option, given the availability and limited cost and toxicity of this metal. − Taking inspiration from iron dependent arene syn -dihydroxylating enzymes present in nature, − iron coordination complexes have been largely explored as catalysts, − and a few examples provide synthetically valuable yields (Figure ). − A common limitation of these reactions in terms of sustainability is that they operate in volatile and toxic solvents, most often acetonitrile.…”

Section: Introductionmentioning

confidence: 99%

Greening Oxidation Catalysis: Iron Catalyzed Alkene syn-Dihydroxylation with Aqueous Hydrogen Peroxide in Green Solvents

Borrell

Costas

2018

ACS Sustainable Chem. Eng.

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Herein, we disclose the application of green solvents in a biologically inspired oxidation reaction. In a mixture of propylene carbonate and ethyl acetate, iron catalyzed syn-dihydroxylation of olefins with aqueous hydrogen peroxide proceeds in short reaction times with excellent yields and chemoselectivity. The current report showcases the suitability of this sustainable media to this class of important reactions.

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cis-Dihydroxylation of electron deficient olefins catalysed by an oxo-bridged diiron(III) complex with H2O2

Cited by 8 publications

References 45 publications

Oxidation of Ferric Xylenol Orange Chelates by Hydrogen Peroxide in Aqueous Solution: Conception of Oxygen Singlet Atoms Generation From Hydrogen Peroxide

Oxidation of Ferric Xylenol Orange Chelates by Hydrogen Peroxide in Aqueous Solution: Conception of Oxygen Singlet Atoms Generation From Hydrogen Peroxide

Mechanistic Insights into Iron-Catalyzed C–H Bond Activation and C–C Coupling

Greening Oxidation Catalysis: Iron Catalyzed Alkene syn-Dihydroxylation with Aqueous Hydrogen Peroxide in Green Solvents

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