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Oxidation of organic compounds including natural products catalysed by transitions metals: Mn, Os and Cu

Grant number: 06/03996-6
Support type:Regular Research Grants
Duration: November 01, 2006 - December 31, 2009
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Organic Chemistry
Principal researcher:Dalmo Mandelli
Grantee:Dalmo Mandelli
Home Institution: Faculdade de Química. Pontifícia Universidade Católica de Campinas (PUC-CAMP). Campinas , SP, Brazil


Oxidation of organic compounds has been extensively studied during the last decades. The products of oxidation, alcohols, ketones and epoxides, are key raw materials for a wide variety of chemicals, polymers and fragrance. Much effort has been done to develop new catalysts for these reactions, using cleaner process that generates smaller amounts of by-products, so-called “green-process”. The aim of this work is to study kinetic parameters on the oxidation of cyclohexane with H2O2 and t-BuOOH, at mild conditions, using metal transition complexes based on Mn, Os and Cu as catalysts. The most active system will be applied on the epoxidation of hexen-1-ene and natural products as terpenes, finding in large amount on Brazilian plants. Oxidation of isopropanol will be also studied. Mechanistic studies will be performed to propose the active specie of the catalyst. In a last step, the main complexes will be heterogeneized on inorganic support as SiO2, Al2O3 or TiO2. (AU)

Scientific publications (10)
(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)
SHUL'PIN, GEORGIY B.; KOZLOV, YURIY N.; SHUL'PINA, LIDIA S.; CARVALHO, WAGNER A.; MANDELLI, DALMO. Oxidation reactions catalyzed by osmium compounds. Part 4. Highly efficient oxidation of hydrocarbons and alcohols including glycerol by the H2O2/Os-3(CO)(12)/pyridine reagent. RSC ADVANCES, v. 3, n. 35, p. 15065-15074, 2013. Web of Science Citations: 19.
MANDELLI, DALMO; KOZLOV, YURIY N.; CARVALHO, WAGNER A.; SHUL'PIN, GEORGIY B. Oxidations by the system `hydrogen peroxide-[Mn2L2O3](2+) (L=1,4,7-trimethyl-1,4,7-triazacyclononane)-carboxylic acid' Part 13. Epoxidation of methyl oleate in acetonitrile solution [1]. Catalysis Communications, v. 26, p. 93-97, SEP 5 2012. Web of Science Citations: 8.
KUZNETSOV, MAXIM L.; KOZLOV, YURIY N.; MANDELLI, DALMO; POMBEIRO, ARMANDO J. L.; SHUL'PIN, GEORGIY B. Mechanism of Al3+-Catalyzed Oxidations of Hydrocarbons: Dramatic Activation of H2O2 toward O-O Homolysis in Complex [Al(H2O)(4)(OOH)(H2O2)](2+) Explains the Formation of HO center dot Radicals. Inorganic Chemistry, v. 50, n. 9, p. 3996-4005, MAY 2 2011. Web of Science Citations: 40.
SHUL'PIN, GEORGIY B.; KOZLOV, YURIY N.; SHUL'PINA, LIDIA S.; STRELKOVA, TATYANA V.; MANDELLI, DALMO. Oxidation of Reactive Alcohols with Hydrogen Peroxide Catalyzed by Manganese Complexes. CATALYSIS LETTERS, v. 138, n. 3-4, p. 193-204, SEP 2010. Web of Science Citations: 33.
KIRILLOVA, MARINA V.; KIRILLOV, ALEXANDER M.; MANDELLI, DALMO; CARVALHO, WAGNER A.; POMBEIRO, ARMANDO J. L.; SHUL'PIN, GEORGIY B. Mild homogeneous oxidation of alkanes and alcohols including glycerol with tert-butyl hydroperoxide catalyzed by a tetracopper(II) complex. JOURNAL OF CATALYSIS, v. 272, n. 1, p. 9-17, MAY 25 2010. Web of Science Citations: 65.
SHUL'PIN, GEORGIY B.; KOZLOV, YURIY N.; SHUL'PINA, LIDIA S.; KUDINOV, ALEXANDER R.; MANDELLI, DALMO. Extremely Efficient Alkane Oxidation by a New Catalytic Reagent H2O2/Os-3(CO)(12)/Pyridine. Inorganic Chemistry, v. 48, n. 22, p. 10480-10482, NOV 16 2009. Web of Science Citations: 106.
MANDELLI‚ D.; DO AMARAL‚ A.C.N.; KOZLOV‚ Y.N.; SHUL’PINA‚ L.S.; BONON‚ A.J.; CARVALHO‚ W.A.; SHUL’PIN‚ G.B. Hydrogen peroxide oxygenation of saturated and unsaturated hydrocarbons catalyzed by montmorillonite or aluminum oxide. CATALYSIS LETTERS, v. 132, n. 1, p. 235-243, 2009.
MANDELLI‚ D.; CHIACCHIO‚ K.C.; KOZLOV‚ Y.N.; SHUL’PIN‚ G.B. Hydroperoxidation of alkanes with hydrogen peroxide catalyzed by aluminium nitrate in acetonitrile. Tetrahedron Letters, v. 49, n. 47, p. 6693-6697, 2008.
MANDELLI‚ D.; KOZLOV‚ Y.N.; GOLFETO‚ C.C.; SHUL’PIN‚ G.B. Peroxyacetic acid oxidation of olefins and alkanes catalyzed by a dinuclear manganese (IV) complex with 1‚ 4‚ 7-trimethyl-1‚ 4‚ 7-triazacyclononane. CATALYSIS LETTERS, v. 118, n. 1, p. 22-29, 2007.

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