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A process for the preparation of the nitrile compound of the carbonitriding method (by machine translation)

The present invention provides a method for the preparation of nitrile compounds cyanide, the organic halide or to be halide with a readily available and inexpensive CO2 , NH3 And a reducing agent, in the presence of a transition metal catalyst of selective carbonitriding reaction, to obtain the target product with a nitrile compound. In the present invention using a brand-new reaction route, through the metal catalytic CO2 And the NH3 The reaction, “one-pot” directly realize halide and intended to halide removing (intended to be) […], avoids the need to use the traditional cyano reaction equivalent highly toxic cyanide issues, at the same time provides a direct, the new method of preparing isotope-labeled nitrile compounds, can be used for medical, tracing, in biological and pharmaceutical research. (by machine translation)

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

 

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Stereoselective synthesis of tetrahydropyran-3-ones by rearrangement of oxonium ylides generated from metal carbenoids

The synthesis of tetrahydropyran-3-ones by copper-catalysed reactions of diazo ketone tethered allylic ethers has been explored. Product distribution can be explained by the intermediacy of a free ylide or direct rearrangement of a metal-bound ylide equivalent.

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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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Oxyfunctionalization of hydrocarbons by in situ formed peracid or by metal assisted aerobic oxidation

The oxidation of hydrocarbons such as adamantane, cyclohexane, tetraline and indane has been investigated using the oxygen/3-methylbutanal system in the presence and in the absence of metal catalyst. The reactivity order reflects the facility of hydrogen abstraction from the substrate.

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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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Synthesis of CuO and Cu2O nano/microparticles from a single precursor: Effect of temperature on CuO/Cu2O formation and morphology dependent nitroarene reduction

CuO and Cu2O nano/microparticles with pure phases have been synthesized from the same precursor by a hydrothermal method. Hydrothermal heating of Cu(OAc)2 produced CuO at 125 C whereas pure Cu2O was obtained at 175 C. Heating at 150 C gave a CuO/Cu2O mixture. In contrast, Cu(acac)2 produced only Cu2O at all three temperatures. The pure phases of Cu2O and CuO nano/microparticles were confirmed by PXRD and XPS characterization. The mechanistic studies indicate that decomposition of the organic anion/ligand of the Cu-precursor played a key role in the formation of CuO/Cu2O nano/microparticles from Cu(OAc)2/Cu(acac)2. FE-SEM studies revealed the formation of CuO with a microsphere morphology (125 C) and a micro-cup for Cu2O at 175 C. Nanowires and micron-sized elliptical cylinders were observed for Cu2O synthesized from Cu(acac)2. However, calcination of Cu(OAc)2, Cu(acac)2 and Cu(NO3)2 at 500 C produced crystalline CuO nano/microparticles with various sizes and morphologies. Further, CuO nano/microparticles investigated for industrially important aromatic nitro to amine conversion showed morphology dependent nitro group reduction. Smaller spherical CuO nano/microparticles obtained from Cu(acac)2 exhibited the highest catalytic activity. The reusability studies indicate that CuO nano/microparticles can be used for up to six cycles. Thus we have presented a simple method to synthesize Cu2O or CuO from the same precursor and demonstrated the morphology dependent catalytic activity of CuO nano/microparticles.

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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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Desymmetrization of meso-N-sulfonylaziridines with chiral nonracemic nucleophiles and bases

The cyclohexene-derived aziridine 7-tosyl-7-azabicyclo[4.1.0]heptane (1) reacts with Grignard reagents in the presence of chiral nonracemic Cu-catalysts to afford sulfonamides 3a-e in up to 91% ee under optimized conditions. No activation of the aziridine by Lewis acids is required. The reaction may be extended to other bicyclic N-sulfonylated aziridines, but aziridines derived from acyclic olefins, cyclooctene, and trinorbornene are unreactive under standard conditions. Exposure of 1 to s-BuLi in the presence of (-)-sparteine (2.8 equiv.) affords the allylic sulfonamide 31 in 35% yield and 39% ee. Under the same conditions, the aziridines 33 and 35 yield products 34 and 36 derived from intramolecular carbenoid insertion with 75 and 43% ee, respectively.

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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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Copper-catalyzed cyclopropanation of 1,2,3,4-tetrahydropyridin-2-ones with diazoacetates: A facile and stereoselective synthesis of 3-oxo-2-azabicyclo [4.1.0] heptanes

The reactions of a series of 1,2,3,4-tetrahydropyridin-2-ones (1) with diazoacetates (2) in the presence of copper-bronze catalyst yielded exclusively 3-oxo-2-azabicyclo [4.1.0] heptanes (3 and 4) in excellent yields with high exo-selectivity. Tetrahydropyridin-2-ones (1) with N-alkyl substituents were found to be more reactive than N-aryl substitutents. Among the various copper catalysts studied, copper(II) triflate was found to be the best catalyst while rhodium chloride, ruthenium chloride did not catalyze the reaction. The application of ultrasonic radiation enhanced the reaction rate and allowed the reactions to be conducted at room temperature.

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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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Mechanistic Insights on Pd/Cu-Catalyzed Dehydrogenative Coupling of Dimethyl Phthalate

Despite its industrial importance, very limited mechanistic information on the dehydrogenative coupling of dimethyl phthalate has been reported. Herein we report the detailed mechanism for dehydrogenative coupling of dimethyl phthalate catalyzed by [Pd(OAc)2]/[Cu(OAc)2]/1,10-phenanthroline¡¤H2O (phen¡¤H2O). The solution-phase analysis of the catalytic system by XANES shows the active species to be Pd(II), and EXAFS supports the formation of an (acetato)(dimethyl phthalyl)(phen)palladium(II) complex from [Pd(OAc)2]. A formation pathway of tetramethyl 3,3?,4,4?-biphenyltetracarboxylate via disproportionation of independently prepared [Pd(OAc){C6H3(CO2Me)2-3,4}(phen)] is observed with regeneration of [Pd(OAc)2(phen)].

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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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Structural characterisation of metal complexes containing 1-[(4-methylphenyl)sulfonamido]-2-[(2-pyridylmethylene)amino]benzene

The interaction of 2-pyridinecarboxaldehyde with N-tosyl-1,2-diaminobenzene leads to the isolation of two different products, {3-[ethoxy(2-pyridyl)methyl]-1-[(4-methylphenyl)sulfonyl]-2-(2-pyridyl)-2,3- dihydro-1H-benzo[d]imidazole}, L1, and {1-[(4-methylphenyl)sulfonyl]-2-(2-pyridyl)-2,3-dihydro-1H-benzo[d] imidazole}, L2, but not to the expected Schiff base 1-[(4-methylphenyl)sulfonamido]-2-[(2-pyridylmethylene)amino]benzene, HL3. Two kinds of complexes, containing the potentially tridentate and monoanionic [L3]- as a ligand, were obtained by different routes. ML3(p-Tos)(H2O)n complexes (p-TosH = p-toluenesulfonic acid; M = Co, Cu, Zn; n = 1-3) have been isolated by electrolysis of a solution phase composed of L1 and p-toluenesulfonic acid, using metal plates as the anode. Metal complexes of composition ML32(H2O)n (M = Mn, Co, Cu, Zn; n = 0-2) were obtained by template synthesis from M(acac)2, 2-pyridinecarboxaldehyde and N-tosyl-1,2-diaminobenzene. All these compounds have been characterised by elemental analyses, magnetic measurements, IR, mass spectrometry and, in the case of M = Zn, by 1H NMR spectroscopy. CuL3(p-Tos)(H2O), 1, ZnL3(p-Tos)(H2O), 2, CoL32, 3, CuL32, 4 and ZnL32 ¡¤ 2CH3CN, 5, were also crystallographically characterised.

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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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Stereocontrol in a ytterbium triflate-catalyzed 1,3-dipolar cyclo-addition reaction of carbonyl ylide with N-substituted maleimides and dimethyl fumarate

The addition of Yb(OTf)3 (10 mol%) in a Rh2(OAc)4-catalyzed reaction of o-(methoxycarbonyl)-alpha-diazoacetophe-none with N-methylmaleimide in CH2Cl2 or in diethyl ether gave cycloadducts with high endo-selectivity (endo:exo = 95:5-96:4). The CuOTf (20 mol%)-or CuCl-Yb(OTf)3 (5 mol%)-catalyzed reaction also gave 1,3-dipolar cycloadducts in an endo-selective manner (endo:exo = 94:6). On the other hand, a reaction using only Rh2(OAc)4 (5 mol%) as the catalyst in benzene under reflux gave cycloadducts with exo-selectivity (endo:exo = 11:89). The reaction of N-ethyland N-phenylmaleimides under the same conditions showed a similar tendency in terms of the stereoselectivity.

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