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Oxidation of metallic copper with complexones in organic media

Direct oxidation of copper in organic media with complexones (sterically hindered o-quinones; acetylacetone and pyridine as stabilizing ligands) was studied. From the complexes obtained, the initial components can be regenerated.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Composition-controlled catalysis of reduced graphene oxide supported CuPd alloy nanoparticles in the hydrolytic dehydrogenation of ammonia borane

Addressed herein is the composition-controlled catalysis of CuPd alloy nanoparticles (NPs) supported on reduced graphene oxide (RGO) in the hydrolytic dehydrogenation of ammonia borane (AB). Nearly monodisperse CuPd alloy NPs were synthesized by using a surfactant-assisted organic solution phase protocol comprising the co-reduction of acetylacetonate complexes of Pd and Cu by morpholine borane complex in oleylamine and 1-octadecene at 80 C. The presented recipe allowed us to make a composition control over the CuPd alloy NPs. Three different compositions of CuPd alloy NPs (2.7 nm Cu30Pd70, 2.9 nm Cu48Pd52, 3.0 nm Cu75Pd25) could be prepared among which the Cu75Pd25 NPs showed the best catalytic performance in hydrogen generation from the hydrolysis of AB. Among the various support materials tested for as-prepared Cu75Pd25 alloy NPs, the RGO-Cu75Pd25 catalysts showed the highest performance in the hydrolysis of AB. Moreover, the activity of the RGO-Cu75Pd25 catalysts were dramatically enhanced by annealing them at 400 C for 1 h under Ar-H2 (5% H2) gas flow and an unprecedented TOF value of 29.9 min-1 was obtained in the hydrolysis of AB at room temperature. The reported TOF value here is much higher than RGO-Cu (TOF = 3.61 min-1) and even higher than RGO-Pd catalysts (TOF = 26.6 min-1). The detailed kinetics of RGO-Cu75Pd25 catalyzed AB hydrolysis was also studied depending on catalyst concentration, substrate concentration and temperature. The apparent activation energy of the catalytic hydrolysis of AB was calculated to be 45 ¡À 3 kJ mol-1.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Crystal structure-selective formation and carrier dynamics of type-II CdS-Cu31S16 heterodimers

Anisotropically phase-segregated CdS-Cu31S16 heterodimers with type-II band alignment were spontaneously formed by selective growth of monoclinic Cu31S16 phases on preformed hexagonal CdS phases. The photo-induced carrier dynamics of the heterodimer was investigated by fluorescence and transient absorption measurements. The Royal Society of Chemistry 2013.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Fura-2FF-based calcium indicator for protein labeling

We describe the synthesis and fluorescence properties of a Fura-2FF-based fluorescent Ca2+ indicator that can be covalently linked to SNAP-tag fusion proteins and retains its Ca2+ sensing ability after coupling to protein. The Royal Society of Chemistry 2010.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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A new protocol for the in situ generation of aromatic, heteroaromatic, and unsaturated diazo compounds and its application in catalytic and asymmetric epoxidation of carbonyl compounds. Extensive studies to map out scope and limitations, and rationalization of diastereo- and enantioselectivities

A variety of metalated tosylhydrazone salts derived from benzaldehyde have been prepared and were reacted with benzaldehyde in the presence of tetrahydrothiophene (THT) (20 mol %) and Rh2(OAc)4 (1 mol %) to give stilbene oxide. Of the lithium, sodium, and potassium salts tested, the sodium salt was found to give the highest yield and selectivity. This study was extended to a wide variety of aromatic, heteroaromatic, aliphatic, alpha,beta-unsaturated, and acetylenic aldehydes and to ketones. On the whole, high yields of epoxides with moderate to very high diastereoselectivities were observed. A broad range of tosylhydrazone salts derived from aromatic, heteroaromatic, and alpha,beta-unsaturated rated aldehydes was also examined using the same protocol in reactions with benzaldehyde, and again, good yields and high diastereoselectivities were observed in most cases. Thus, a general process for the in situ generation of diazo compounds from tosylhydrazone sodium salts has been established and applied in sulfur-ylide mediated epoxidation reactions. The chiral, camphor-derived, [2.2.1] bicyclic sulfide 7 was employed (at 5-20 mol % loading) to render the above processes asymmetric with a range of carbonyl compounds and tosylhydrazone sodium salts. Benzaldehyde tosylhydrazone sodium salt gave enantioselectivities of 91 ¡À 3% ee and high levels of diastereoselectivity with a range of aldehydes. However, tosylhydrazone salts derived from a range of carbonyl compounds gave more variable selectivities. Although those salts derived from electron-rich or neutral aldehydes gave high enantioselectivities, those derived from electron-deficient or hindered aromatic aldehydes gave somewhat reduced enantioselectivities. Using alpha,beta-unsaturated hydrazones, chiral sulfide 7 gave epoxides with high diastereoselectivities, but only moderate yields were achieved (12-56%) with varying degrees of enantioselectivity. A study of solvent effects showed that, while the impact on enantioselectivity was small, the efficiency of diazo compound generation was influenced, and CH3CN and 1,4-dioxane emerged as the optimum solvents. A general rationalization of the factors that influence both relative and absolute stereochemistry for all of the different substrates is provided. Reversibility in formation of the betaine intermediate is an important issue in the control of diastereoselectivity. Hence, where low diastereocontrol was observed, the results have been rationalized in terms of the factors that contribute to the reduced reversion of the syn betaine back to the original starting materials. The enantioselectivity is governed by ylide conformation, facial selectivity in the ylide reaction, and, again, the degree of reversibility in betaine formation. From experimental evidence and calculations, it has been shown that sulfide 7 gives almost complete control of facial selectivity, and, hence, it is the ylide conformation and degree of reversibility that are responsible for the enantioselectivity observed. A simple test has been developed to ascertain whether the reduced enantioselectivity observed in particular cases is due to poor control in ylide conformation or due to partial reversibility in the formation of the betaine.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Vinylogous Wolff Rearrangement of Cyclic beta,gamma-Unsaturated Diazomethyl Ketones: a New Synthetic Method for Angularly Functionalised Polycyclic Systems

Decomposition of the rigid polycyclic beta,gamma-unsaturated diazomethyl ketones (1a) and (1b) and (2a) and (2b) promoted by ‘activated CuO’, Cu(acac)2, Cu(OTf)2, or Ni(acac)2 in the presence of methanol are shown to give mainly the corresponding rearranged gamma,delta-unsaturated angularly substituted esters (3a) and (3b) and (8a) and (8b) together with the alpha-methoxy ketones (4a) and (4b) and (9a) and (9b).While photo-Wolff rearrangement of the diazo ketones leads to the corresponding homologous esters (5a) and (5b) and (10a) and (10b) the silver benzoate-triethylamine induced reaction gives the rearranged esters in addition to the homologous esters.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Standard enthalpies of formation and combustion of a crystalline copper complex with tetramethyltetraethylporphine

The heat of combustion of a copper complex with 2,7,12,17-tetramethyl-3,8,13,18-tetraethylporphine was measured in an isothermal liquid calorimeter with a stationary calorimetric bomb. The standard enthalpies of combustion and formation of the complex studied were calculated (DeltacH =-21694.77 ¡À 12.54 kJ/mol, DeltafH = 3796.59 ¡À 12.60 kJ/mol).

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Ligand-free copper-catalyzed arylation of imidazole and N,N?-carbonyldiimidazole, and microwave-assisted synthesis of N-Aryl-1H-imidazoles

Microwave-assisted arylation of 1H-imidazoles and N,N?- carbonyldiimidazole under ligand-free copper-mediated conditions in tetraethyl orthosilicate is reported. Valuable evidence for understanding of the Cu-catalyzed mechanism of the Ullmann reaction is also presented.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Binuclear copper complexes with CuICuI and Cu+1.5Cu+1.5 core structures formed in the reactions of 3?(2?methylbutyl)?5?pyridylmethylene?2?thiohydantoin with copper(II) acetylacetonate and copper(II) chloride

A treatment of the ligands, 3?(2?methylbutyl)?5?pyridylmethylene-substituted 2?thio?3,5?dihydro?4??imidazole?4?one (L) with CuCl2¡¤2H2O in MeOH/CH2Cl2 or Cu(acac)2 in MeOH/CH2Cl2 affords to binuclear complexes with the [L-H]2Cu+1.5Cu+1.5Cl or [L-H]2CuICuI composition, respectively. X-ray crystallography demonstrated close Cu-Cu interaction for the first complex and the absence of Cu?Cu bonding for the second one.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Preparation of Cu Thin Films by the Decomposition of Copper Acetylacetonate on Catalytically Active Substrate Surfaces

A selective CVD system used to deposit the central metal of a volatile complex preferentially on catalytically active substrate surfaces was examined.Copper(II) acetylacetonate was vaporized in a flow of hydrogen and decomposed on Ni, Pd, and Al plates in order to deposit metallic copper.When a Ni plate was used as the substrate, deposition of metallic copper occurred at temperatures in the range 130-180 deg C only on the substrate surfaces.The formation of an ultrathin film of Cu of uniform thickness was confirmed.On a Pd substrate, the formation of an ultrathin Cu film of uniform thickness was also observed.On an Al substrate, however, deposition occurred nonselectively at temperatures above 160 deg C, not only on the substrate surface, itself, but also on the wall of the glass tube as well as the quartz wool surrounding the Al plate.In addition, the formation of fine particles of Cu, instead of thin film, was found to exist on the substrate.Because the deposition of Cu took place on catalytically active surfaces selectively, the deposition was considered to proceed by a catalytic hydrogenation of the C=O bond of the ligand, thus detaching it from the Cu ion and allowing it to decompose the complex and deposit Cu metal.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”