3.2.3. Hydroformylation 2467 3.2.4. Dimerization 2468 3.2.5. Oxidative Cleavage and Ozonolysis 2469 3.2.6. Metathesis 2470 4. Terpenes 2472 4.1. Pinene 2472 4.1.1. Isomerization: R-Pinene 2472 4.1.2. Epoxidation of R-Pinene 2475 4.1.3. Isomerization of R-Pinene Oxide 2477 4.1.4. Hydration of R-Pinene: R-Terpineol 2478 4.1.5. Dehydroisomerization 2479 4.2. Limonene 2480 4.2.1. Isomerization 2480 4.2.2. Epoxidation: Limonene Oxide 2480 4.2.3. Isomerization of Limonene Oxide 2481 4.2.4. Dehydroisomerization of Limonene and Terpenes To Produce Cymene 2481

Chemical Routes for the Transformation of Biomass into Chemicals

Free radical functionalization of organic compounds catalyzed by N-hydroxyphthalimide.

Structural and functional evolution of metallacrowns.

Aromatic molecules are key constituents of many pharmaceuticals, electronic materials, and commodity plastics. The utility of these molecules directly reflects the identity and pattern of substituents on the aromatic ring. Here, we report a palladium(II) catalyst system, incorporating an unconventional ortho-dimethylaminopyridine ligand, for the conversion of substituted cyclohexanones to the corresponding phenols. The reaction proceeds via successive dehydrogenation of two saturated carbon-carbon bonds of the six-membered ring and uses molecular oxygen as the hydrogen acceptor. This reactivity demonstrates a versatile and efficient strategy for the synthesis of substituted aromatic molecules with fundamentally different selectivity constraints from the numerous known synthetic methods that rely on substitution of a preexisting aromatic ring.

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Palladium-Catalyzed Aerobic Dehydrogenation of Substituted Cyclohexanones to Phenols

Polymer-supported Schiff base complexes in oxidation reactions

The catalytic activity of the molybdenum catalysts, molybdenum naphthenate, Mo(CO)6, H2[Mo2O4(ox)2(H2O)2]·4H2O·Me2CO, Mo(O)2(acac)2, and [Mo(O)2(SAP)(EtOH)], was investigated in the reaction of oleic acid epoxidation by organic hydroperoxides. A new highly efficient and selective system for the epoxidation of unsaturated aliphatic acids was developed with tert-butyl hydroperoxide (t-BuOOH) and the [Mo(O)2(SAP)(EtOH)] complex. The epoxidation reaction of oleic acid shows 86.8% selectivity to 9,10-epoxystearic acid at 67% conversion of t-BuOOH. Routine kinetic measurements were performed to determine the reaction orders with respect to t-BuOOH and the catalyst. They are 1.00±0.05 and 0.51±0.05, respectively. The activation energy and enthalpy, Ea=99±4 kJ mol−1 and ΔH=96±4 kJ mol−1, were calculated from the temperature dependences. The results allowed us to propose a reaction mechanism whose outline is consistent with the generally accepted mechanism of the catalytic epoxidation of olefins by organic hydroperoxides.

Molybdenum complex-catalysed epoxidation of unsaturated fatty acids by organic hydroperoxides

The catalytic epoxidation of olefins with organic hydroperoxides

New insights into the chemistry of oxomolybdenum(VI) complexes with N-salicylidene-2-aminoethanol

New efficient aerobic oxidation of some alcohols with dioxygen catalysed by N-hydroxyphtalimide with vanadium co-catalysts

Protonation and copper(II) coordination properties of kanamycin A were studied in solution by potentiometry, UV-Vis, circular dichroism (CD), EPR and cyclic voltammetry (CV) Only mononuclear complexes of stoichiometries ranging from CuH2L to CuH−2L were found Kanamycin A anchors Cu(II) ions with an {NH2, O−} chelate of the C-ring of its molecule At pH higher than 6 the amino and hydroxyl groups of the A-ring of kanamycin A also participate in binding The resulting structure, similar to that of complexes of other unsubstituted aminoglycosides studied previously, involves Cu(II) coordination by donors of terminal aminosugar rings, rather than those of the central unit The results of cyclic voltammetry investigations, kinetic studies of H2O2 disproportionation and ROS detection experiments, further supported the mechanism of oxidative reactivity of cupric complexes of aminoglycosides, proposed by us recently [M Jezowska-Bojczuk, W Leśniak, W Bal, H Kozlowski, K Gatner, A Jezierski, J Sobczak, S Mangani and W Meyer-Klaucke; Chem Res Toxicol, 2001, 14, 1353–1362], which involves Cu(I) and Cu(III) redox states and both metal-bound and free ROS

Jarosław M. Sobczak

Papers

Molybdenum complex-catalysed epoxidation of unsaturated fatty acids by organic hydroperoxides

The catalytic epoxidation of olefins with organic hydroperoxides

New insights into the chemistry of oxomolybdenum(VI) complexes with N-salicylidene-2-aminoethanol

New efficient aerobic oxidation of some alcohols with dioxygen catalysed by N-hydroxyphtalimide with vanadium co-catalysts

Copper(II) binding by kanamycin A and hydrogen peroxide activation by resulting complexes