Metal-Catalyzed Oxidation of C-H Compounds with Peroxides in Unconventional Solvents

This chapter describes some examples of oxidation of C-H compounds (saturated and aromatic hydrocarbons and alcohols) with peroxides catalyzed by various metal compounds (mainly coordination complexes). The nature of the solvent plays a very important role in these reactions: the yield of products and selectivity can be dramatically changed when one solvent is replaced by another one. Adding certain cocatalysts to the reaction solution we can also significantly modify the yield and selectivity. Especially, interesting and attractive are oxidations in "green" solvents, first of all in water. The focus is made on the author's own works

Chapter 4: The Vanadate-Pyrazinecarboxylic Acid-Hydrogen Peroxide Reagent and Similar Systems for Efficient Oxidations with Peroxides

A simple vanadate anion VO3- does not catalyse various oxidations with hydrogen peroxide via the generation of hydroxyl radicals. The addition of pyrazinecarboxylic acid (PCA) dramatically accelerates the oxidation reactions (Shul'pin et al., 1993) via the H2O2 decomposition as confirmed by DFT calculations: the activation barrier of the HȮ formation in the presence of PCA is by 9.6 kcal mol-1 lower than that in the absence of PCA. In contrast to the oxidation of methane in acetonitrile by the reagent hydrogen peroxide-vanadate anion-pyrazine-2-carboxylic acid (PCA), carrying out the process in an aqueous solution is accompanied by intensive parallel destruction of the co-catalyst (PCA). Therefore, relatively high yields of methane oxidation products (mainly formic acid) can only be achieved at a sufficiently high concentration of PCA. Additives of strong acids (sulphuric, trifluoroacetic and perchloric) increase the yield of products. It has been found that perchloric acid can also be used as a co-catalyst instead of PCA. Some strong inorganic and organic acids added to the aqueous solution noticeably increase the yield of formic acid as the main product of methane oxygenation. © Royal Society of Chemistry 2021

Oxidations By The Reagent O2-h2o2-vanadium Complex - Pyrazine-2-carboxylic Acid. Part 7. Hydroperoxidation Of Higher Alkanes

Alkanes (n-heptane, 2- and 3-methylhexane, cis- and trans-decalin) are readily oxidized under air in acetonitrile by the O2-H2O2-PCA-VO3 - reagent at room temperature to produce alkyl hydroperoxides as main products as well as minor amounts of the corresponding alcohols and carbonyl compounds. The site selectivities of the reactions are very similar to those observed with hydroxylation of the alkanes with hydrogen peroxide under UV irradiation. The proposed mechanism involves the catalytic formation of hydroxyl radicals from hydrogen peroxide which abstract hydrogen atoms from the alkanes. The alkyl radicals react rapidly with molecular oxygen to produce peroxyl radicals which are transformed mainly into the hydroperoxides.52411305113062Patai, S., (1983) The Chemistry of Peroxides, , Wiley: ChichesterDrauz, K., Waldmann, H., (1995) Enzyme Catalysis in Organic Synthesis, , VCH: New York-WeinheimJefford, C.W., (1993) Chem. Soc. Rev., p. 59Shul'pin, G.B., (1988) Organic Reactions Catalyzed by Metal Complexes, , Nauka: MoscowDrago, R.S., (1992) Coord. Chem. Rev., 117, p. 185Barton, D.H.R., Doller, D., (1992) Acc. Chem. Res., 25, p. 504Strukul, G., (1992) Catalytic Oxidations with Hydrogen Peroxide as Oxidant, , Kluwer: DordrechtBarton, D.H.R., Martell, A.E., Sawyer, D.T., (1993) The Activation of Dioxygen and Homogeneous Catalytic Oxidation, , Plenum: New YorkSchuchardt, U., Carvalho, W.A., Spinacé, E.V., (1993) Synlett, p. 713Oyama, S.T., Hightower, J.W., (1993) Catalytic Selective Oxidation, , ACS: WashingtonCrabtree, R.H., (1995) Chem. Rev., 95, p. 987Shilov, A.E., Shul'pin, G.B., (1995) Activation and Catalytic Reactions of Hydrocarbons, , Nauka: MoscowShul'pin, G.B., Attanasio, D., Suber, L., (1993) Russ. Chem. Bull., 42, p. 55Shul'pin, G.B., Druzhinina, A.N., Nizova, G.V., (1993) Russ. Chem. Bull., 42, p. 1326Nizova, G.V., Shul'pin, G.B., (1994) Russ. Chem. Bull., 43, p. 1146Shul'pin, G.B., Süss-Fink, G., (1995) J. Chem. Soc., Perkin Trans. 2, 2, p. 1459Shul'pin, G.B., Drago, R.S., Gonzalez, M., (1996) Russ. Chem. Bull, 45, p. 10Guerreiro, M.C., Schuchardt, U., Shul'pin, G.B., Russ. Chem. Bull., , submitted for publicationNizova, G.V., Süss-Fink, G., Shul'pin, G.B., unpublished resultsGalimova, L.G., Maslennikov, S.I., Nikolaev, A.I., (1980) Bull. Acad. Sci. USSR, Div. Chem. Sci., 29, p. 1731Baxendale, J.H., Wilson, J.A., (1957) Trans. Faraday Soc., 53, p. 344Sawyer, D.T., (1991) Oxygen Chemistry, p. 126. , Oxford University Press: New York, cap. 5, 128Russel, G.A.J., (1957) J. Am. Chem. Soc., 79, p. 3871Reid, I.D., Rhodes, C.J., Roduner, E., (1992) Tetrahedron Lett., 33, p. 561

Oxidation of C-H compounds with peroxides catalyzed by polynuclear transition metal complexes in Si- or Ge-sesquioxane frameworks: A review

Polynuclear transition metal complexes in Si- or Ge-sesquioxane frameworks synthesized in recent years turned out to be efficient catalysts in oxidation of organic compounds with peroxides: H2O2, tert-butyl hydroperoxide (TBHP), meta-chloroperoxybenzoic acid (MCPBA). This brief review describes oxygenations by peroxides of alkanes to alkyl hydroperoxides, alcohols and ketones and benzene to phenol as well as oxidation of alcohols to the corresponding ketones. Some reactions with MCPBA occur stereoselectively. © 2017 Elsevier B.V

Oxidation With The "o2-h2o2-vo3 --pyrazine-2-carboxylic Acid" Reagent: 6. * Oxidation Of N-heptane And Cyclohexane. Direct Determination Of Alkyl Hydroperoxides By Gas-liquid Chromatography

n-Heptane is readily oxidized in acetonitrile under the action of H2O2 with a "vanadate anion-pyrazine-2-carboxylic acid" system as the catalyst in air to form isomeric heptyl hydroperoxides (detected by GLC) along with isomeric heptanols and heptanones. Heptyl hydroperoxides slowly decompose at low temperature yielding the corresponding alcohols and ketones (aldehyde). The values of the parameter of the relative normalized reactivity of the H atoms at the carbon atoms in positions 1, 2, 3, and 4 depend on the reaction time and concentrations of the reagents. The value of the parameter of selectivity C(1) : C(2) : C(3) : C(4) varies in the range from 1.0 : 2.8 : 2.9 : 1.8 to 1.0 : 5.6 : 5.9 : 5.3. The low selectivity of the reaction shows that the key role is played by the attack of highly reactive radical particles on the C-H bond of the alkane molecule.464749754Shul'pin, G.B., Drago, R.S., Gonzalez, M., (1996) Izv. Akad. Nauk, Ser. Khim., p. 2514(1996) Russ. Chem. Bull., 45, p. 2386. , Engl. TranslShul'pin, G.B., Attanasio, D., Suber, L., (1993) Izv. Akad. Nauk. Ser. Khim., p. 64(1993) Russ. Chem. Bull., 42, p. 55. , Engl. TranslShul'pin, G.B., Attanasio, D., Suber, L., (1993) J. Catal., 142, p. 147Shul'pin, G.B., Druzhinina, A.N., Nizova, G.V., (1993) Izv. Akad. Nauk, Ser. Khim., p. 1394(1993) Russ. Chem. Bull., 42, p. 1326. , Engl. TranslNizova, G.V., Shul'pin, G.B., (1994) Izv. Akad. Nauk, Ser. Khim., p. 1212(1994) Russ. Chem. Bull., 43, p. 1146. , Engl. TranslShul'pin, G.B., Süss-Fink, G., (1995) J. Chem. Soc., Perkin Trans. 2, p. 1459Shul'pin, G.B., Guerreiro, M.C., Schuchardt, U., (1996) Tetrahedron, 52, p. 13051Emanuel', N.M., Gal, D., (1984) Okislenie Etilbenzola [Oxidation of Ethylbenzene], , Nauka, Moscow, 280 pp. (in Russian)Shul'pin, G.B., Bochkova, M.M., Nizova, G.V., (1995) J. Chem. Soc., Perkin Trans. 2, p. 1465Shul'pin, G.B., Nizova, G.V., Kozlov, Yu.N., (1996) New J. Chem., 20, p. 1243Nizova, G.V., Süss-Fink, G., Shul'pin, G.B., (1997) J. Chem. Soc., Chem. Commun., p. 397Nizova, G.V., Süss-Fink, G., Shul'pin, G.B., (1997) Tetrahedron, 53, p. 3603Aveline, B.A., Kochevar, I.E., Redmond, R.W., (1996) J. Am. Chem. Soc., 118, p. 289Sheu, C., Richert, S.A., Cofré, P., Ross B., Jr., Sobkowiak, A., Sawyer, D.T., Kanofsky, J.R., (1990) J. Am. Chem. Soc., 112, p. 1936Sheu, C., Sobkowiak, A., Zhang, L., Ozbalik, N., Barton, D.H.R., Sawyer, D.T., (1989) J. Am. Chem. Soc., 111, p. 8030Ellis P.E., Jr., Lyons, J.E., (1990) Coord. Chem. Rev., 105, p. 181Schuchardt, U., Krähembühl, C.E.Z., Carvalho, W.A., (1991) New J. Chem., 15, p. 955Goldstein, A.S., Drago, R.S., (1991) J. Chem. Soc., Chem Commun., p. 21Kao, L.-C., Hutson, A.C., Sen, A., (1991) J. Am. Chem. Soc., 113, p. 700Lin, M., Sen, A., (1992) J. Am. Chem. Soc., 114, p. 7307Sen, A., Lin, M., (1992) J. Chem. Soc., Chem. Commun., p. 508Sen, A., Lin, M., Kao, L.-C., Hutson, A.C., (1992) J. Am. Chem. Soc., 114, p. 6385Schuchardt, U., Carvalho, W.A., Spinacé, E.V., (1993) Synlett, p. 713Labinger, J.A., (1994) Catal. Lett., 26, p. 95Grinstaff, M.W., Hill, M.G., Labinger, J.A., Gray, H.B., (1994) Science, 264, p. 1311Nakata, K., Yamaoka, Y., Miyata, T., Taniguchi, Y., Takaki, K., Fujiwara, Y., (1994) J. Organomet. Chem., 473, p. 329Goldstein, A.S., Beer, R.H., Drago, R.S., (1994) J. Am. Chem. Soc., 116, p. 2424Lin, M., Sen, A., (1994) Nature, 368, p. 613Kurioka, M., Nakata, K., Jintoku, T., Taniguchi, Y., Takaki, K., Fujiwara, Y., (1995) Chem. Lett., p. 244Barton, D.H.R., Taylor, D.K., (1995) Izv. Akad. Nauk, Ser. Khim., p. 595(1995) Russ. Chem. Bull., 44, p. 575. , Engl. TranslBirnbaum, E.R., Grinstaff, M.W., Labinger, J.A., Bercaw, J.E., Gray, H.B., (1995) J. Mol. Catal., A: Chem., 104, pp. L119Shilov, A.E., Shul'pin, G.B., (1995) Aktivatsiya i Kataliticheskie Reaktsii Uglevodorodov [Activation and Catalytic Reactions of Hydrocarbons], , Nauka, Moscow, 400 pp. (in Russian

Oxidation With The "o2 - H2o2 - Vauauium Complex - Pyrazine-2-carboxylic Acid" Reagent 9. Oxidation Of Cyclohexene And Decalin

The oxidation of cyclohexene with hydrogen peroxide catalyzed by a vanadium complex and pyrazine-2-carboxylic acid (PCA) in air results in the formation of cyclohex-2-enyl hydroperoxide as the main product and cyclohex-2-enol, cyclohex-2-enone, cyclohex-3-enyl hydroperoxide, cyclohex-3-enol, cyclohexanol, cyclohexane, and 1,2-epoxycyclohexane in lesser amounts. The composition of the products of oxidation of decalin isomers with the system in question is similar to those obtained in the photochemical oxidation with hydrogen peroxide in air and in the oxidation with air in the presence of anthraquinone. A proposed mechanism for the oxidation includes the initiation by hydroxyl radicals generated from hydrogen peroxide under the action of the V - PCA system.472247252Nizova, G.V., Süss-Fink, G., Shul'pin, G.B., (1997) Tetrahedron, 53, p. 3603Shilov, A.E., Shul'pin, G.B., (1995) Aktivatsiya i Kataliticheskie Reaktsii Uglevodorodov [Activation and Catalytic Reactions of Hydrocarbons], , Nauka, Moscow, 400 pp. (in Russian)Shilov, A.E., Shul'pin, G.B., (1997) Chem. Rev., , in pressShul'pin, G.B., Attanasio, D., Suber, L., (1993) Izv. Akad. Nauk, Ser. Khim., p. 64(1993) Russ. Chem. Bull., 42, p. 55. , Engl. TranslShul'pin, G.B., Druzhinina, A.N., Nizova, G.V., (1993) Izv. Akad. Nauk, Ser. Khim., p. 1394(1993) Russ. Chem. Bull., 42, p. 1326. , Engl. TranslNizova, G.V., Shul'pin, G.B., (1994) Izv. Akad. Nauk, Ser. Khim., p. 1212(1994) Russ. Chem. Bull., 43, p. 1146. , Engl. TranslShul'pin, G.B., Süss-Fink, G., (1995) J. Chem. Soc., Perkin Trans., 2, p. 1459Shul'pin, G.B., Drago, R.S., Gonzalez, M., (1996) Izv. Akad. Nauk, Ser. Khim., p. 2514(1996) Russ. Chem. Bull., 45, p. 2386. , Engl. TranslGuerreiro, M.C., Schuchardt, U., Shul'pin, G.B., (1997) Izv. Akad. Nauk, Ser. Khim., p. 780(1997) Russ. Chem. Bull., 46, p. 749. , Engl. TranslShul'pin, G.B., Guerreiro, M.C., Schuchardt, U., (1996) Tetrahedron, 52, p. 13051Shul'pin, G.B., Attanasio, D., Suber, L., (1993) J. Catal., 142, p. 147Shul'pin, G.B., Nizova, G.V., (1992) React. Kinet. Catal. Lett., 48, p. 333Nizova, G.V., Süss-Fink, G., Shul'pin, G.B., (1997) Chem. Commun., p. 397Day, V.W., Klemperer, W.G., Yagasaki, A., (1990) Chem. Lett., p. 1267Baxendale, J.H., Wilson, J.A., (1957) Trans. Faraday Soc., 53, p. 344Rontani, J.-F., Giusti, G., (1990) J. Photochem. Photobiol., A: Chem., 53, p. 69Mimoun, H., Saussine, L., Daire, E., Postel, M., Fischer, J., Weiss, R., (1983) J. Am. Chem. Soc., 105, p. 3101Barton, D.H.R., Hu, B., Li, T., MacKinnon, J., (1996) Tetrahedron Lett., 37, p. 8329Shul'pin, G.B., Druzhinina, A.N., (1992) React. Kinet. Catal. Lett., 47, p. 207Shul'pin, G.B., Nizova, G.V., (1995) Mendeleev Commun., p. 143Shul'pin, G.B., Nizova, G.V., Kozlov, Yu.N., (1996) New J. Chem., 20, p. 1243Barton, D.H.R., Béviére, S.D., Chavasiri, W., Csuhai, E., Doller, D., (1992) Tetrahedron, 48, p. 2895Barton, D.H.R., Béviére, S.D., Chavasiri, W., Csuhai, E., Doller, D., Liu, W.-G., (1992) J. Am. Chem. Soc., 114, p. 2147Bateman, L., Gee, G., (1951) Trans. Faraday Soc., 47, p. 155Russel, G.A., (1957) J. Am. Chem. Soc., 79, p. 3871Mimoun, H., Chaumette, P., Mignard, M., Saussine, L., (1983) Nouv. J. Chim., 7, p. 467Mimoun, H., Mignard, M., Brechot, P., Saussine, L., (1986) J. Am. Chem. Soc., 108, p. 3711Mimoun, H., (1983) Isr. J. Chem., 23, p. 451Butler, A., Clague, M.J., Meister, G.E., (1994) Chem. Rev., 94, p. 625Neumann, R., De La Vega, M., (1993) J. Mol. Cat., 84, p. 93Bonchio, M., Conte, V., Di Furia, F., Modena, G., Moro, S., (1994) J. Org. Chem., 59, p. 626

Oxidation of C-H compounds with peroxides catalyzed by polynuclear transition metal complexes in Si- or Ge-sesquioxane frameworks: A review

Polynuclear transition metal complexes in Si- or Ge-sesquioxane frameworks synthesized in recent years turned out to be efficient catalysts in oxidation of organic compounds with peroxides: H2O2, tert-butyl hydroperoxide (TBHP), meta-chloroperoxybenzoic acid (MCPBA). This brief review describes oxygenations by peroxides of alkanes to alkyl hydroperoxides, alcohols and ketones and benzene to phenol as well as oxidation of alcohols to the corresponding ketones. Some reactions with MCPBA occur stereoselectively. © 2017 Elsevier B.V

Homogeneous oxidation of C–H bonds with m-CPBA catalysed by a Co/Fe system: mechanistic insights from the point of view of the oxidant

Oxidations of C–H bonds with m-chloroperoxybenzoic acid (m-CPBA) catalyzed by transition metal complexes are known to proceed through a number of routes, from the non-selective free radical to selective concerted and metal-mediated ones. However, there is a lack of understanding of the m-CPBA oxidative behavior, reaction mechanisms and factors that trigger its activity. An experimental and theoretical investigation of sp3 C–H bond oxidation with m-CPBA in the presence of the heterometallic pre-catalyst [CoIII4FeIII2O(Sae)8]·4DMF·H2O (1) (H2Sae = salicylidene-2-ethanolamine) and HNO3 promoter has been performed herein. The catalytic system 1/HNO3/m-CPBA allows mild hydroxylation of tertiary C–H bonds with 99% retention of stereoconfiguration of model alkane substrates, supported by high TOFs up to 2 s−1 (for cis-1,2-dimethylcyclohexane) and TONs up to 1.4 × 104 (at 50 °C). The catalytic effect of 1 is seen at the ppm level, while 1000 ppm (0.1 mol%) loading allows 1000-fold increase of the initial reaction rate up to 9 × 10−5 M s−1. The reaction mechanism was investigated by means of combined kinetic studies (including isotope effects), isotopic labeling (18O2, H218O, D2O), ESI-MS spectroscopy and DFT theoretical studies. The results suggest that the main oxidation pathway proceeds through a concerted mechanism involving a cobalt-peroxo C–H attacking species or via a cobalt–oxyl species (rebound process), rather than a free-radical pathway. Remarkably, the Co(iii) catalyst does not change its oxidation state during the most energetically favored pathway, consistent with a metal–ligand cooperativity. The chlorobenzene radical is responsible for H abstraction in the non-selective side route, which is efficiently suppressed by the acidic promoter. Finally, signs for slow direct oxygen exchange between m-CPBA and water in the presence of a proton or a metal complex are found, suggesting that the results of 18O-tests should be treated cautiously when m-CPBA is used as the oxidant. This journal is © The Royal Society of Chemistr