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Copper-Catalyzed Oxidative Self-Coupling of alpha-Amino Carbonyl Compounds for the Synthesis of Tetrasubstituted 1,4-Enediones

A protocol for the copper-catalyzed oxidative self-coupling of alpha-amino carbonyl compounds has been developed for the synthesis of tetrasubstituted 1,4-enediones (Z -isomers) in moderate to good yields through the cleavage of four sp 3 C-H bonds and the simultaneous formation of one C=C double bond in the alpha-amino carbonyl compound. The strategy has the advantages of using readily available starting materials and of high stereoselectivity.

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

 

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Copper(II) complex with acetylacetone phenylhydrazone: Synthesis, crystal structure, and thermal stability

The Cu(phac)2 complex was synthesized by the reaction of copper(II) acetate with acetylacetone phenylhydrazone (Hphac), and its crystal structure was established by X-ray diffraction: space group P21/c, a = 11.173(3) A, b = 8.267(2) A, c = 12.633(4) A, beta = 115.01(3), V = 1057.5(5) A3, Z = 4, R1 = 0.0476. The crystal structure of Cu(phac)2 consists of the centrosymmetrical mononuclear molecules. The central copper(II) ion is coordinated by two oxygen atoms and two nitrogen atoms of two acetylacetone phenylhydrazone ligands. The Cu(phac)2 molecules are linked in layers parallel to the Oyz plane. The oxygen atoms of the ketone fragment are involved in intermolecular bonding, which completes the coordination sphere of the central copper(II) ion to a substantially elongated octahedron. The thermal stability of the Cu(phac)2 complex was estimated under nitrogen at atmospheric pressure and in vacuo.

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

 

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Synthesis, characterization and fungicidal activity of binary and ternary metal(II) complexes derived from 4,4?-((4-nitro-1,2-phenylene) bis(azanylylidene))bis(3-(hydroxyimino)pentan-2-one)

Ternary copper(II) and binary copper(II), nickel(II) and cobalt(II) complexes derived from 4,4?-((4-nitro-1,2-phenylene)bis(azanylylidene))bis(3-(hydroxyimino)pentan-2-one) (H2L) were synthesized and characterized by elemental and thermal analyses, IR, UV-Vis. and 1H NMR spectroscopy, conductivity and magnetic moments measurements. The analytical and spectral data showed that, the ligand acts as dibasic tetradentate or dibasic hexadentate bonding to the metal ion via the two-imine nitrogen, two nitrogen and/or oximato oxygen atoms of deprotonated oxime groups forming five and/or six rings including the metal ions. The complexes adopt either tetragonal distorted octahedral or square planar geometry around metal ions. The ESR spectra of the solid copper(II) complexes are characteristic to d9 configuration and having an axial symmetry type of a d(x2-y2) ground state. The g values confirmed the geometry is elongated tetragonal octahedral geometry with considerably ionic or covalent environment. The antifungal biological activity of the prepared compounds was studied using well diffusion method. The obtained results showed that, the ligand is biologically inactive while its metal complexes were more potent fungicides than the ligand and standard antifungal drug (Amphotericin B).

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

 

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Preparation of epitaxial YBa2Cu3O7-y films on CeO2-buffered yttria-stabilized zirconia substrates by fluorine-free metalorganic deposition

Epitaxial YBa2Cu3O7-y (YBCO) films of 120-550 nm thickness have been prepared by fluorine-free metalorganic deposition using a metal acetylacetonate-based coating solution on yttria-stabilized zirconia (YSZ) substrates with an evaporated CeO2 buffer layer. The YBCO films were highly (0 0 1)-oriented by X-ray diffraction theta-2theta scanning and phi{symbol} scanning. The YBCO films 120-400 nm in thickness demonstrated high critical current densities (Jc) with an average in excess of 3 MA/cm2 at 77 K using an inductive method. In particular, a 210-nm-thick film showed a Jc of 4.5 MA/cm2. These excellent properties are attributed to the high crystallinity, small in-plane fluctuation due to high epitaxy and to the microstructure free from grain boundaries in the YBCO films. Further increase of film thickness increased the fraction of irregularities, i.e., precipitates and micropores, in the film surfaces, resulting in lower Jc values.

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

 

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Kinetic features of catalytic decomposition of cyclohexyl hydroperoxide and 1-methylcyclohexyl hydroperoxide

Catalytic decomposition of cyclohexyl and 1-methylcyclohexyl peroxides in the presence of 3d-metal acetylacetonates was studied.

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

 

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A Copper-Catalyzed Tandem C?H ortho-Hydroxylation and N?N Bond-Formation Transformation: Expedited Synthesis of 1-(ortho-Hydroxyaryl)-1H-indazoles

A facile, one-pot synthesis of 1H-indazoles featuring a Cu-catalyzed C?H ortho-hydroxylation and N?N bond-formation sequence with the use of pure oxygen as the terminal oxidant was developed. The reaction of readily available 2-arylaminobenzonitriles with various organometallic reagents led to ortho-arylamino N?H ketimine species. Subsequent Cu-catalyzed hydroxylation at the ortho position of the aromatic ring followed by N?N bond formation in DMSO under a pure-oxygen atmosphere afforded a wide variety of 1-(ortho-hydroxyaryl)-1H-indazoles in good to excellent yields. This efficient method does not require the utilization of noble-metal catalysts, elaborate directing groups, or privileged ligands.

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

 

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Synthesis and characterization of bis (acetylacetonato kappa-O, O?) [zinc(ii)/copper(ii)] hybrid organic-inorganic complexes as solid metal organic precursors

We have synthesized novel metal organic hybrid mixed compounds of bis (acetylacetonato kappa-O, O?) [zinc(ii)/copper(ii)]. Taking C10H14O4Zn0.7Cu0.3 (Z0.7C0.3AA) as an example, the crystals are composed of Z0.7C0.3AA units and uncoordinated water molecules. Single-crystal X-ray diffraction results show that the complex Z0.7C0.3AA crystallizes in the monoclinic system, space group P21/n. The unit cell dimensions are a = 10.329(4) A, b = 4.6947(18) A, and c = 11.369(4) A; the angles are alpha = 90, beta = 91.881(6), and gamma = 90, the volume is 551.0(4) A3, and Z = 2. In this process, the M(ii) ions of Zn and Cu mix and occupy the centers of symmetrical structural units, which are coordinated to two ligands. The measured bond lengths and angles of O-M-O vary with the ratio of metal species over the entire series of the complexes synthesized. The chemistry of the as-synthesized compounds has been characterized using infrared spectroscopy, mass spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis, and the morphology of the products has been characterized using scanning electron microscopy. The thermal decomposition of the Z0.7C0.3AA composites measured by thermogravimetric analysis suggests that these complexes are volatile. The thermal characteristics of these complexes make them attractive precursors for metal organic chemical vapor deposition.

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

 

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One-pot synthesis of monodisperse copper?silver alloy nanoparticles and their composition-dependent electrocatalytic activity for oxygen reduction reaction

Development of an economical, well-defined and efficient electrocatalyst having a potential to replace Pt/C is crucial for oxygen reduction reaction (ORR). In this respect, we report herein one-pot wet-chemical protocol for the composition-controlled synthesis of monodisperse CuAg alloy nanoparticles (NPs) and their composition-dependent electrocatalytic activities in ORR for the first time under an alkaline condition. The presented synthetic procedure yields CuAg NPs that exhibit monodisperse size distribution with an average particle diameter of ?8 nm. Almost homogenous CuAg alloy formation is proved by using many advanced analytical techniques despite the considerable lattice mismatch between Cu and Ag. At all compositions investigated, the ORR activities of CuAg electrocatalysts are found to be significantly higher than monometallic Ag NPs. Improved ORR kinetics of CuAg alloy NPs are demonstrated by Tafel slopes (85 mV/dec for Cu30Ag70, 84 mV/dec for Cu40Ag60 and 78 mV/dec for Cu60Ag40 which are all smaller than that of monometallic Ag (113 mV/dec). Electrochemical impedance measurements support these findings and represent that charge transfer resistance strongly depends on composition of CuAg electrocatalyst. The ORR activity and surface analysis results put Cu40Ag60 forward since Cu oxidation is suppressed in Cu40Ag60 NPs, caused by Ag enhancement in the surface.

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

 

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X-ray crystal structures of copper(II) and cobalt(II) complexes with Schiff base ligands. Reactivity towards dioxygen

Copper(II) and cobalt(II) Schiff base complexes with derivatives of the pentadentate ligand bis(salicylideneimino-3-propyl)amine [H2salDPT] have been prepared. The X-ray crystal structures of the copper(II) complexes Cu[salDPT] and Cu[sal(n-propyltrimethylsilyl)DPT] were determined and revealed five-coordination at the metal centre in both cases. The 1:1 dioxygen adduct of Co[sal(n-propyltrimethylsilyl)DPT] was also isolated and its X-ray molecular structure determined.

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

 

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A gas-chromatographic study of the thermodynamic characteristics of the interaction of sorbates with combined liquid phases prepared from polyethylene glycol and metal acetylacetonates

The thermodynamic characteristics of the interaction between sorbates and combined liquid phases for gas chromatography were determined. The phases were prepared from polyethylene glycol-20M modified with copper, aluminum, and nickel acetylacetonates.

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