The Dual Roles of Oxodiperoxovanadate Both as a Nucleophile and an Oxidant in the Green Oxidation of Benzyl Alcohols or Benzyl Halides to Aldehydes and Ketones

Li, Chunbao; Zheng, Pengwu; Li, Jie; Zhang, Hang; Cui, Yi; Shao, Qing; Ji, Xiujie; Zhang, Jian; Zhao, Pengying; Xü, Yanli

doi:10.1002/anie.200351902

Cited by 79 publications

(19 citation statements)

References 27 publications

(19 reference statements)

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“…As with the oxidation of alkanes in acetonitrile catalyzed by vanadate ions, the oxidation of isopropanol in isopropanol as a solvent occurs at a much lower rate in the absence of pyrazinecarboxylic acid (see works on the oxidation of alcohols catalyzed by vanadium derivatives [20][21][22][23][24][25][26]). …”

Section: Resultsmentioning

confidence: 99%

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The kinetics and mechanism of oxidation of isopropanol with the hydrogen peroxide-vanadate ion-pyrazine-2-carboxylic acid system

Romakh

Kozlov

Süß‐Fink

et al. 2007

Russ. J. Phys. Chem.

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INTRODUCTIONWe found earlier that the V vanadate anion effectively catalyzed the oxidation of saturated and aromatic hydrocarbons with hydrogen peroxide in acetonitrile in air at temperatures of from 20 to 70°C [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. The necessary condition for the reaction to occur was the presence of pyrazine-2-carboxylic acid (PCA) as a cocatalyst in concentrations several times higher than the concentration of the vanadium complex. The primary products of the oxidation of alkanes were alkylhydroperoxides, which decomposed during the reaction to the corresponding carbonyl compound (ketone or aldehyde) and alcohol. At the initial stage of the reaction, especially at a low temperature, only alkylhydroperoxides were detected in solutions. Benzene was transformed into phenol. A study of the selectivity of oxidation of various alkanes showed that the oxidative action of the system under consideration was caused by the generation of hydroxyl radicals, which attacked hydrocarbon C-H bonds [13,14].According to [14], pyrazinecarboxylic acid facilitated proton transfer between separate ligands in the coordination sphere of vanadium and thereby accelerated the decomposition of the vanadium peroxo complex with PCA. This increased the rate of the generation of hydroxyl radicals. Recently, this system was studied theoretically by the density functional theory (DFT) method [19]. It was shown that, indeed, direct proton O 3 -transfer from the H 2 O 2 molecule to the oxygen atom of the vanadium-containing particle required overcoming a barrier much higher than when a proton migrated from hydrogen peroxide first to the carboxyl group of the pyrazine-2-carboxylic acid anion (coordinated to the vanadium ion at the nitrogen atom) and then to the V=O fragment.In this work, we for the first time studied the mechanism of oxidation of isopropanol in the system specified by spectral and kinetic methods. Oxidation was performed in the substrate itself as a solvent and in acetonitrile. We also compared the oxidation of isopropanol with the oxygenation of cyclohexane in acetonitrile. EXPERIMENTALOxidation reactions were performed in air in a glass cylindrical temperature-controlled vessel. The reaction solution volume was 10 ml. Reaction solution samples (0.6 ml) were taken in certain time intervals. After treatment with excess solid triphenylphosphine for 10 min, the samples were analyzed by gas-liquid chromatography. Hydrogen peroxide was introduced as a 30% aqueous solution from Fluka (not stabilized).A DANI-86.10 chromatograph with a 25 m × 0.32 mm × 0.25 µ m capillary column, a CP-WAX52CB carrier, and an SP-4400 integrator was used; the carrier gas was helium. Chromatograms were calibrated Romakh a, b , Yu. N. Kozlov a , G. Süss-Fink b , and G Abstract -The vanadate anion in the presence of pyrazine-2-carboxylic acid (PCA) was found to effectively catalyze the oxidation of isopropanol to acetone with hydrogen peroxide. The electronic spectra of solutions and the kinetics of oxidation were s...

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Section: Resultsmentioning

confidence: 99%

“…The interaction of the vanadium(IV) derivative with a new hydrogen peroxide molecule (possibly with the formation of a new diperoxo complex) results in the generation of the hydroxyl radical, (25) or, in a simpler form,…”

Section: Resultsmentioning

confidence: 99%

The kinetics and mechanism of oxidation of isopropanol with the hydrogen peroxide-vanadate ion-pyrazine-2-carboxylic acid system

Romakh

Kozlov

Süß‐Fink

et al. 2007

Russ. J. Phys. Chem.

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“…These results demonstrate the importance of protons in catalytic process. Many vanadium catalysts have been presented in the literature for a variety of oxidations: alcohol oxidations, [38] olefin epoxidation, [1,[39][40][41] sulfide oxidation, [6,7,9,11,41] and phosphane oxidation. [1,8] Many of these processes use in-situ-derived catalytic systems from vanadium starting materials, vanadyl sulfate and vanadyl acetylacetonate being the most common, with a variety of ligands.…”

Section: Discussionmentioning

confidence: 99%

Mechanistic Analysis of Nucleophilic Substrates Oxidation by Functional Models of Vanadium‐Dependent Haloperoxidases: A Density Functional Theory Study

et al. 2007

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Density functional theory has been used to investigate the structural, electronic, and reactivity properties of an established functional model for vanadium‐dependent haloperoxidases, K[VO(O2)Hheida] (Hheida2– = 2,2′‐[(2‐hydroxyethyl)imino]diacetate). Possible solution species were determined on the basis of potential exogenous donors present under the conditions necessary for reactivity. The energetically favored solution‐state species is a 1:1 complex of Hheida and vanadium with a coordinated hydroxyethyl donor trans to the vanadium–oxido bond which is in agreement with the reported solid‐state structure for K[VO(O2)Hheida]. Transition states of the oxidation reaction were located for four substrates: chloride, bromide, iodide, and dimethyl sulfide. The role of protonation and its effects on reactivity were examined for each substrate. Protonation of the peroxido moiety leads to a significant drop in the activation barrier for oxidation. In contrast no transition states could be located for an oxido‐transfer process involving the oxido ligand. Barriers of activation calculated for halide oxidation were similar, providing support to the hypothesis that the pKa of the halide in acetonitrile is responsible for the decrease in reactivity between I–, Br–, and Cl–. The results presented herein provide a mechanistic correlation between a functional model and the enzyme, making K[VO(O2)Hheida] a “complete” functional model for vanadium‐dependent haloperoxidase.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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“…Quite recently, a mechanism was published related to benzyl alcohols or benzyl halides oxidation to aldehydes and ketones, with V 2 O 5 and H 2 O 2 at pH = 4. 17 To note, those authors report in the text that a diperoxido vanadium species is operating with a nucleophilic character but the reactivity they observed is strongly enhanced at pH 1. Furthermore, when we treated toluene with H 2 O 2 -VO 3 − at pH = 4 (where diperoxido vanadium species is present), no reaction at all occurred.…”

Section: Dalton Transactions Papermentioning

confidence: 94%

A sustainable two-phase procedure for V-catalyzed toluene oxidative bromination with H2O2–KBr

2013

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A sustainable V(V) and Mo(VI) catalysed two-phase procedure for bromination of toluene under quite mild conditions is proposed; H 2 O 2 is the primary oxidant and KBr is the bromine source; metal precursors are commercially available salts. The reaction is efficient without any additional solvent. By using PhCH 3 as a solvent/substrate good yields, together with interesting selectivity toward the formation of PhCH 2 Br, are obtained with both metal ions. Recycling of the catalytic phase is also possible. Useful information on the V-peroxido chemistry was obtained.

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The Dual Roles of Oxodiperoxovanadate Both as a Nucleophile and an Oxidant in the Green Oxidation of Benzyl Alcohols or Benzyl Halides to Aldehydes and Ketones

Cited by 79 publications

References 27 publications

The kinetics and mechanism of oxidation of isopropanol with the hydrogen peroxide-vanadate ion-pyrazine-2-carboxylic acid system

The kinetics and mechanism of oxidation of isopropanol with the hydrogen peroxide-vanadate ion-pyrazine-2-carboxylic acid system

Mechanistic Analysis of Nucleophilic Substrates Oxidation by Functional Models of Vanadium‐Dependent Haloperoxidases: A Density Functional Theory Study

A sustainable two-phase procedure for V-catalyzed toluene oxidative bromination with H2O2–KBr

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