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Abstract Oxidation of sulfides to sulfoxides and oxidative coupling of thiols into their corresponding disulfides were carried out using hydrogen peroxide (H2O2) as oxidizing agent in the presence of immobilized Ni, Co, Cr, Zn or Cd complexes on Fe3O4 magnetic nanoparticles (M-Salen-MNPs) as stable, heterogeneous, efficient and magnetically recoverable nanocatalysts under mild reaction conditions. These supported complexes were characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). A variety of aromatic and aliphatic sulfides and thiols with different functional groups were successfully oxidized with short reaction times in good to excellent yields. Recovery of the catalyst is easily achieved by magnetic decantation and reused for several consecutive runs without significant loss of its catalytic efficiency.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Compositions for enhancing the penetration of pharmacologically active agents through skin comprising a sugar ester in combination with a sulfoxide or phosphine oxide.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A series of flavin-cyclodextrin conjugates has been prepared and tested in the enantioselective oxidations of prochiral aromatic and aliphatic sulfides with hydrogen peroxide. The newly prepared conjugates contain isoalloxazinium or alloxazinium moieties attached to the primary rim of alpha- and beta-cyclodextrins at the C-6 positions. In addition, flavinium units were attached to the secondary rim of the beta-cyclodextrin macrocycle. The relationship between the structural features and the catalytic performance of the conjugates, including those recently reported by us, was analyzed. The rate and enantioselectivity of the sulfoxidations catalyzed by flavin-cyclodextrin conjugates are influenced mainly by the size of the cyclodextrin cavity, the type of flavin unit (alloxazine or isoalloxazine), and by the relative orientation of the flavin and cyclodextrin moieties.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A quantitative and gentle oxidation (combustion) of hydrogen in the presence of oxygen in a variety of solvents was achieved under palladium on carbon (Pd/C)-catalyzed conditions at ordinary pressures and temperatures. A quantitative generation of water accountable for the consumed oxygen was observed. While hydrogen peroxide (H2O2), which would form as an intermediate, was extremely unstable under the Pd/C-catalyzed conditions to be converted into water with accompanying oxygen generation, the stability of H2O2 was found to be increased in cold (0 C) trifluoroacetic acid, and the formation of 64% H2O2 based on the consumed oxygen could be detected. A mechanistic elucidation study revealed that the single electron transfer and generation of the hydroxyl radical are involved in the gentle combustion process. The reactive oxygen species generated during the process was effectively utilized for the chemical oxidation of sulfides and phosphines to afford the corresponding sulfoxides and phosphine oxides, respectively.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Several acyclic alpha-chlorosulfoxides have been shown to undergo a gamma-dehydrochlorination upon treatment with LDA.The proposed immediate products of gamma-dehydrochlorination, thiirane-S-oxides, are unstable under the basic conditions and react further with the LDA; the isolated products are usually E-alkenes and (or) E-vinyl sulfoxides.Some of the proposed intermediate thiirane-S-oxides, compounds 6, 7, 8, and 18, were synthesized independently and treated with one equivalent of LDA in order to mimic the second step of the overall dehydrochlorination/ring opening sequence.The products obtained from the reactions of compounds 6 and 18 compared favourably with those products which were believed to arise from certain conformations of alpha-chlorosulfoxides 1kB and 1e, respectively.Tha addition of one equivalent of LDA to 1kA afforded a mixture containing thiirane-S-oxide 8, which is proposed as the immediate product of gamma-dehydrochlorination of 1kA.The configurations of 1kB and 1hA were both shown to be threo by X-ray crystallographic studies.Those conformations which are preferred for the dehydrochlorination possess a geometry where the sulfinyl oxygen is anti to any of the substituents of the ring carbons.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A simple and efficient method for the synthesis of 5-substituted tetrazoles, sulfides and sulfoxides in the presence of Pd(0) complex immobilized on mesoporous SBA-15 as an efficient, recoverable and thermally stable mesostructure has been reported. Also, the prepared mesostructure was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray mapping, energy-dispersive X-ray spectroscopy, N2 adsorption and desorption, inductively coupled plasma optical emission spectroscopy and thermal gravimetric analysis. Then, this mesostructured catalyst was applied in the synthesis of 5-substituted tetrazoles, sulfides and sulfoxides. The approach described here offers advantages such as short reaction times, high yield, purity yields, simple and eco- friendly, easy work-up. More importantly, this nanohybrid robust catalyst did not undergo metal leaching and applied several times without any decrease in catalytic activity.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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An artificial metalloenzyme (BSA-CoL) based on the incorporation of a cobalt(ii) Schiff base complex {CoL, H2L = 2,2?-[(1,2-ethanediyl)bis(nitrilopropylidyne)]bisphenol} with bovine serum albumin (BSA) has been synthesized and characterized. Attention is focused on the catalytic activity of this artificial metalloenzyme for enantioselective oxidation of a variety of sulfides with H2O2. The influences of parameters such as pH, temperature, and the concentration of catalyst and oxidant on thioanisole as a model are investigated. Under optimum conditions, BSA-CoL as a hybrid biocatalyst is efficient for the enantioselective oxidation of a series of sulfides, producing the corresponding sulfoxides with excellent conversion (up to 100%), chemoselectivity (up to 100%) and good enantiomeric purity (up to 87% ee) in certain cases.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Four structurally different alloxazine-cyclodextrin conjugates were prepared and tested as catalysts for the enantioselective oxidation of prochiral sulfides to sulfoxides by hydrogen peroxide in aqueous solutions. The alloxazinium unit was appended to the primary face of alpha- and beta-cyclodextrins via a linker with variable length. A series of sulfides was used as substrates: n-alkyl methyl sulfides (n-alkyl = hexyl, octyl, decyl, dodecyl), cyclohexyl methyl sulfide, tert-butyl methyl sulfide, benzyl methyl sulfide and thioanisol. alpha-Cyclodextrin conjugate having alloxazinium unit attached via a short linker proved to be a suitable catalyst for oxidations of n-alkyl methyl sulfides, displaying conversions up to 98% and enantioselectivities up to 77% ee. beta-Cyclodextrin conjugates were optimal catalysts for the oxidation of sulfides carrying bulkier substituents; e.g. tert-butyl methyl sulfide was oxidized with quantitative conversion and 91% ee. Low loadings (0.3-5 mol%) of the catalysts were used. No overoxidation to sulfones was observed in this study.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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In the present study, we report the synthesis of two green recoverable catalysts by covalent linking of the creatinine La and Pr complexes on an MCM-41 mesostructure with the commercially available materials and via a simple and inexpensive procedure. These heterogeneous catalysts were characterized by Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, N2 adsorption and desorption, inductively coupled plasma optical emission spectroscopy, and thermogravimetric analysis. The obtained mesostructures act as active and reusable catalysts for the oxidation of sulfides and oxidative coupling of thiols under neat conditions. More importantly, significant practical advantages of this environmentally friendly process include high efficiency, good reaction times, and convenient recovery and reusability for several times without any significant loss of activity of the catalyst.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Alkyl, aryl and cyclic sulfides are rapidly oxidized to the corresponding sulfoxides in high yields upon microwave thermolysis with iron(III) nitrate impregnated on clay (clayfen) under solvent-free conditions; the conversion also occurs in refluxing methylene chloride but requires much longer reaction time.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method