The role of the Baeyer–Villiger reaction in the liquid-phase oxidation of organic compounds

The data on the composition of ester products formed in the Baeyer–Villiger reaction in the liquid-phase oxidation of organic compounds with molecular oxygen, on production channel of peroxy acids, as well as on the influence of a carbonyl compound structure on its reactivity in reactions with peroxy acids have been classified and considered. The Baeyer–Villiger reaction was shown to be the main source of accessory primary alcohol esters and lactones in industrial processes of aerobic oxidation of cyclohexane and paraffin hydrocarbons.     

The Baeyer–Villiger oxidation of ketones: A paradigm for the role of soft Lewis acidity in homogeneous catalysis

The Baeyer–Villiger oxidation of ketones to the corresponding esters or lactones is a valuable transformation that has been upgraded several times over the last century, from the original use of monopersulfuric acid as oxidant to more atom efficient and environmentally friendly oxidants such as hydrogen peroxide. The latter requires activation with organometallic complexes to explicate its oxidizing power. The catalytic version of the reaction can be achieved with several transition metal catalysts, but major differences are present among the various catalysts proposed in terms of scope of the reaction. In particular, most of the catalytic systems are active towards four-membered ring ketones leading to the corresponding substituted γ-butyro-lactones. Pt^II complexes characterized by the employment of chelating diphosphines turned out to be the most efficient in catalyzing the BV oxidation of a wider range of substrates, in particular cyclohexanones are suitable substrates and acyclic ketones can be converted into the corresponding esters, albeit with low turnover. As long as organometallic catalyzed BV reaction is concerned, Pt^II catalysts show the most versatile activity and selectivity. Such peculiar features are the result of the unique electronic properties of such metal combined with an easily tailored soft Lewis acid character modulated by the proper choice of the ancillary ligands. The enantioselective version of the reaction benefits from these properties and the compatibility of Pt^II species with water enabled the development of asymmetric catalytic BV reactions in water aided by the presence of micelles as dynamic self-assembled environments.     

Asymmetric Baeyer—Villiger oxidation: control of stereoelectronic demand

The recent development of asymmetric Baeyer—Villiger oxidation of prochiral and racemic ketones is briefly summarized, focusing on the regio- and stereocontrol of the oxidation attained by regulating the stereoelectronic demand in the step of rearrangement of the Criegee intermediate.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1784–1794, September, 2004.     

Fe–Co/sulfonated polystyrene as an efficient and selective catalyst in heterogeneous Baeyer–Villiger oxidation reaction of cyclic ketones

A highly efficient catalyst Fe–Co/sulfonated polystyrene (Fe–Co/SPS) was introduced and synthesized, which catalyzed BV oxidation of ketones with aqueous hydrogen peroxide to give the corresponding lactones in high yield and selectivity. Solid acid catalyst of Fe–Co/SPS has been prepared by using the 98-wt% sulfuric acid as the sulfonating agent and CoCl₂ combined FeCl₃ as sources of metal ions. Various physical–chemical characterizations including FT-IR, XRD, SEM and TGA, revealed that bimetallic ions Fe³⁺–Co²⁺ species in the sulfonated polystyrene framework were responsible for the catalytic activities. The BV reaction catalyzed by Fe–Co/SPS highlighted the special effects between metal ions and protonic acids as well as solvent-free heterogeneous catalytic oxidation with excellent conversion.     

Influence of hydroperoxides on the enantioselectivity of metal-catalyzed asymmetric Baeyer–Villiger oxidation and epoxidation with chiral ligands

Chiral hydroperoxides have a significant influence on the enantioselectivity of the metal-catalyzed asymmetric Baeyer–Villiger oxidation of cyclic ketones and the epoxidation of allylic alcohols, when chiral ligands are employed. If both the ligand and the hydroperoxide are enantiopure, the ligand determines the formation of the preferred product enantiomer in both reactions.     

Stereoelectronic and steric effect in the Baeyer–Villiger rearrangement of steroidal α-chlorocyclobutanones

The regioselectivity of the Baeyer–Villiger oxidation of α-chlorocyclobutanone derivatives is markedly affected by substituents in position γ to the carbonyl group. The reaction of steroidal α-chlorocyclobutanones with m-chloroperoxybenzoic acid results in the formation of γ-chloro-γ-lactones and/or α-chloro-γ-lactones depending on the substitution pattern of the four-membered ring. In the reactions of γ-unsubstituted α-chlorocyclobutanones, the exclusive formation of γ-chloro-γ-lactone results from the migration of the chlorinated substituent (CHCl) versus the alkyl group (CH₂), contrary to the expected migratory aptitude. In explaining the unusual regioselectivity observed in these reactions, steric effects and dipole interactions in the formation of the reactive Criegee intermediates are considered and the stereoelectronic effect is postulated to be more important than the intrinsic migratory aptitude.     

Pentafluoroperbenzoic acid as the efficient reagent for Baeyer–Villiger oxidation of cyclic ketones

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Polymer-anchored platinum complexes as catalysts for the Baeyer–Villiger oxidation of ketones: preparation and catalytic properties

The preparation of a variety of catalysts obtained by ion exchange of the complex [(dppb)Pt(μ−OH)]₂²⁺ with sulfonated styrene–divinylbenzene copolymers is reported. Copolymers used are commercial ion exchange resins containing either 4% or 20% DVB and they were loaded with either Li⁺ or NBu₄⁺ prior to exchange with the Pt complex. Metal loading in the heterogenized catalysts is in the range 2–8% by weight. Their catalytic properties in the Baeyer–Villiger oxidation of methylcyclohexanone with hydrogen peroxide appear to be best in terms of activity and productivity either in neat ketone or in EtOH as the solvent. The use of commercial resins with high exchange capacity prevents the use of DCE as the solvent, i.e., the optimum conditions for the homogeneous system, thereby leading to activities and productivities that are generally lower than their homogeneous counterpart. A discussion on the influence of the philicity properties of the support with respect to the performance of the catalyst is reported.     

“Matrix effects” in the activation of compounds with a system of conjugation in the inhibition of oxidative processes

Russian Chemical Bulletin -     

The adequacy of the observed kinetic order in catalyst and the differential selectivity patterns to the hypothesis of the cooperative mechanism of catalysis of the Suzuki—Miyaura reaction

The generally accepted mechanism of the Suzuki—Miyaura reaction suggests a sequential activation of the substrate (aryl halide) and the reagent (arylboronic acid) by a palladium catalyst with the formation of unsymmetric biaryl as a result of a single turnover of the catalytic cycle, i.e., it is linear from the kinetic point of view. At the same time, the use of an unconventional kinetic approach based on the analysis of the differential selectivity of the reaction, rather than the regularities of catalytic activity, indicates the inadequacy of the linear mechanism, that is consistent with the hypothesis of a nonlinear (the so-called cooperative) mechanism of catalysis, in which the product is formed as a result of the substrate and reagent activation by two different palladium-containing intermediates in two parallel catalytic cycles. The experimentally observed low kinetic orders of the Suzuki—Miyaura reaction with respect to the concentration of the palladium catalyst precursor under the ligand-free conditions of catalysis are also consistent with the cooperative mechanism and can be due to the changes in the relative amount of the catalyst in two parallel catalytic cycles and/or to the process of catalyst deactivation.

     

Thermodynamic aspects of the Ru(III)—EDTA—ascorbate—molecular oxygen system for the oxidation of saturated and unsaturated organic compounds

The activation and thermodynamic parameters corresponding to rate and equilibrium constants, respectively, for the homogeneous oxidation of the saturated substrates, cyclohexane to cyclohexanol, cyclohexanol to cis-1,3-cyclohexane diol and olefin, cyclohexene to epoxide by Ru(III)—EDTA—ascorbateO₂ system were determined by measuring the various rates and equilibrium constants at four different temperatures in the range 288–313 K and μ = 0.1 M KNO₃ in a 50% (V/V) mixture of 1,4-dioxane and water in acidic medium. The kinetics of the oxidation of these substrates at each particular temperature was studied as a function of the concentration, the substrates, hydrogen ion, catalyst, ascorbic acid and molecular oxygen. The orders of the reaction in cyclohexanol and cyclohexene concentrations are one, and those in cyclohexane and hydrogen ion concentration are fractional and inverse first-order, respectively. For all substrates the reaction is first order with respect to the concentrations of molecular oxygen, ascorbic acid and catalyst. The source of the oxygen atom transferred to the substrates was confirmed by ¹⁸O₂ isotope studies in which the ¹⁸O was incorporated in the oxidized products. The kinetics and solvent isotope effect were studied for the oxidation of C₆H₁₂, C₆D₁₂, C₆H₁₁OH and C₆D₁₁OD. The order of the reactivity observed in the oxidation of the substrates studied is cyclohexene > cyclohexanol > cyclohexane. A comparison of the rates of oxidation of the substrates and the corresponding activation parameters with the catalytic systems Ru(III)—EDTAO₂ and Ru(III)—EDTA—ascorbateH₂O₂ indicated that activation parameters become more favourable in the presence of ascorbic acid, where the system acts as a mono-oxygenase and the activation energies are drastically reduced. Highly negative entropies are associated with all oxygen atom transfer reactions, indicating that the oxidation process is associative in nature.     

Electrochemical and ESR-study of the mechanism of organic compound oxidation in the presence of mediators—Radical cations of substituted pyrazin-di-N-oxydes

The mechanism of methanol, ethanol, diethyl ether, triethyl-o-formate, cyclohexanol, and cyclohexane oxidation in the presence of electrochemically generated radical cations of 2,5-dimethyl-, 2,3,5,6-tetramethyl-, 2,3-dimethyl-5,6-cyclohexa-, and 3-phenyl-5,6-cyclohexapyrazin-di-N-oxydes as mediators was studied by cyclic voltammetry, ESR-electrolysis, and gas chromatography. The studies were carried out at glassy-carbon-, Pt-, and Au-electrodes in 0.1 M LiClO₄ solutions in acetonitrile and methanol, the alcohol being used as a solvent and substrate simultaneously. ESR-spectra of the radical cations of the pyrazin-di-N-oxydes were recorded. Effects of temperature, oxygen, admixtures of water and acid, and the nature of substrate and solvent on the shape of the cyclic voltammograms and intensity of the ESR-spectra of the pyrazin-di-N-oxydes are elucidated. By comparing experimental and calculated voltammograms, the rate constants for the interaction between the pyrazin-di-N-oxydes and the substrates C-H-bonds are determined. Mechanism of the ultimate two-electron catalytic oxidation of the organics as a constituent of complexes, formed with the radical cations of the mediators (pyrazin-di-N-oxydes), is suggested.     

Effect of organic and inorganic compounds on dissolution kinetics of chalcopyrite in hydrogen peroxide– Hydrochloric acid system

The addition of 2-Propanol as an organic substance and NaCl as an inorganic compound in hydrochloric acid with hydrogen peroxide as a strong leaching agent of chalcopyrite was investigated. The effects of the leaching parameters on copper extraction, such as stirring speed, H₂O₂ concentration, temperature, HCl concentration and solid/liquid ratio were studied. The maximum final copper extraction of 54.55% was obtained with 600 rpm stirring speed, 1.5 M H₂O₂, 0.5 M HCl, 600 rpm, 50 °C, 240 min of the reaction and particle size of ?106 +75 µm. Further experiments were performed when the solid-to-liquid ratio (S/L), stirring speed, temperature, HCl, H₂O₂ and leaching time were kept constant to examine the influence of NaCl and 2-Propanol concentrations in the range of 0–0.5 M and 0–3 M, respectively. The results showed that the copper extraction was increased up to 58.11% with addition of NaCl. While copper extraction yield reached 94.25% in case of addition of 2-propanol with the optimum parameters(0.5 M HCl,50 °C, 1.5 M H₂O₂, 600 rpm, particle size ?106 +75 μm, solid liquid ratio 2g/L, 3 M 2-propanol). The chalcopyrite leaching in hydrogen peroxide– hydrochloric acid system was found to be described by the interface transfer and diffusion across the product layer with activation energy of 77.14 kJ/mol. Addition of 2-propanol suggested that the reaction was under product layer diffusion control and decreased the activation energy of chalcopyrite leaching to 67.98 kJ/mol.     

Effect of porosity on the kinetics of the two-route chlorine reaction: The chlorine evolution—ionization kinetics on iridium dioxide

The porosity effect on the kinetics of the chlorine reaction proceeding via two parallel paths is analyzed theoretically. An equation for the steady-state polarization curve is derived for these conditions. The chlorine evolution-ionization kinetics is studied by steady-state polarization measurements at a rotating disk electrode with an active iridium dioxide coating. A comparison of experimental and theoretical polarization curves shows the chlorine reaction to proceed via two parallel paths not only on DSA and RuO₂, but on IrO₂ as well     

Baeyer–Villiger reaction of Wieland–Misher ketone derivatives: an alternative to the dienone–phenol rearrangement

This paper demonstrates the regioselectivity of the Baeyer–Villiger reaction of dicarbonylated compounds such as Wieland–Misher ketone derivatives in favour of oxygen insertion only between the quaternary carbon of the ring junction and the neighbouring carbonyl group. Further reaction sequences allow the formation of various compounds, including phenols and naphtalenones, the later being similar to the result of the dienone-phenol rearrangement of 4-acylcyclohexan-2,5-dienones already described in the literature, as well as 2-carboxy cyclohexenones which might be used as synthons for the synthesis of complex natural products. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASWieland–Misher ketone / Baeyer–Villiger / regioselectivity     

The photolysis of the uranyl oxalate system—III photochemical behaviour,kinetics and mechanism in aqueous solution

The photochemical behaviour, kinetics and mechanism of the uranyl oxalate system, have been studied at 25°C and pH 4.5. The detectable ionic and molecular species after photolysis are UO₂²⁺, U(IV) and CO₂. Kinetic evidence for the participation of an uranyl oxalate (1:2) complex as the primary photo-activatable species, is reported. The suggested photolysis mechanism is in agreement with the quantitative and qualitative results of this investigation and shows similar tendencies to the mechanism suggested for the photolysis in strongly acidic (pH ≤ 1.7) solutions.     

Mechanism of the reaction of 1,1′-diethylferrocene and decamethylferrocene with peroxides in organic solvents

Kinetic relationships of oxidation of 1,1′-diethylferrocene and decamethylferrocene with peroxides ROOR (R = H, t-C₄H₉) in organic solvents were studied and the composition of oxidation products was established. It is shown that reactivity of (C₅H₄C₂H₅)₂Fe is significantly lower than that of Cp*₂Fe [Cp* = η⁵-C₅(CH₃)₅] which is seen from the ability of the first metal complex to undergo oxidation with a notable rate only in the presence of Brønsted acids, whereas the second substance is oxidized both in the presence and in the absence of these acids. Two possible mechanisms of oxidation of metal complexes in the presence of strong acids are discussed. One of them is based on the ability of ferrocene to fast and equilibrium protonation with the formation of Cp₂Fe⁺—H structure. Another one considers the ability of metal complexes to coordinate peroxides with the formation of weakly bound charge transfer complexes of the composition Cp₂Fe^δ+·ROOR^δ-. The possibility of their formation is confirmed by the oxidation of Cp₂Fe with hydroperoxides in the absence of acids.     

Electrochemical oxidation of organosilicon compounds: V. Electrochemical oxidation of α-silyethers. remarkable effect of silicon on oxidation potentials and reaction pathways

Substitution of a silyl group for hydrogen at the α-position of ethers caused a significant decrease in their oxidation potentials. This effect is attributed to an interaction of the carbonsilicon σ-bond with the lone pair of the oxygen atom. The preparative anodic oxidation of α-silylethers proceeded smoothly in methanol and the carbonsilicon bond was selectively cleaved to give the corresponding acetals.     

The complex reaction kinetics of neptunium including redox and extraction process in 30% TBP—nitric acid system

In order to understand the complex and dynamic neptunium process chemistry in the TBP-HNO₃ system, the kinetics involved reversible redox reaction and extraction mass transfer was investigated. The results indicates that the mass transfer rate of Np(VI) is much faster than the redox reaction in aqueous solution. The concentrations of nitric acid and nitrous acid not only can change the Np(V) oxidation reaction and Np(VI) reduction reaction rate, but also can ultimately determine the distribution of neptunium extraction equilibrium. The variety of temperature can only influence the extraction equilibrium time, but cannot alter the equilibrium state of neptunium.