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An efficient dual synthetic manifold for 2-aminofurans and 2-unsubstituted furans has been developed. The carbenoid-mediated [3 + 2] cycloaddition of copper carbenoids with enamines provides 2-amino-2,3-dihydrofurans which serve as common intermediates for both 2-aminofurans and 2-unsubstituted furans. The Royal Society of Chemistry 2012.

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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) 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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Several compounds have been isolated from the reaction between different copper bis(acetylacetonato) derivatives and the potentially bridging ligand 2,3-bis(2-pyridyl)pyrazine (bppz). A compound of formula [Cu(tfacac) 2(bppz)] (1) is obtained when the substituted trifluoromethylacetylacetonato is used. The use of different anions and the unsubstituted acetylacetonato give rise to new derivatives of general formula [{Cu(acac))2(mu-bppz)2]X2 (X– BF4-, 2; PF6-, 3; BPh 4-, 4). In these compounds the bppz ligand is acting as a bridge by chelating one copper atom and bonding monodentate a second copper atom. The presence of anions with different coordination abilities introduces variations in the copper environment and geometry. When the non-coordinating tetraphenylborate is used different compounds depending on the nature of the solvent are obtained. The dimer 4 was isolated from a methanol/chloroform mixture, while in the absence of chloroform the monomeric compound of formula [Cu(acac)(bppz)(ROH)](BPh4)-ROH (ROH=MeOH, 5) was obtained. When ethanol was used instead of methanol the analogous derivative 6 (R=EtOH) was isolated. Both species show a mononuclear structure with the copper atom five-coordinated by the chelating acac and bppz ligands and one hydroxo group occupying the apical position. A similar environment for the copper appears in [Cu(tfacac)(bppz)(MeOH)](BPh4), 7, which shows a dimeric structure through hydrogen bonds interactions. The magnetic susceptibility data of the dimeric compounds show very weak antiferromagnetic interactions between the copper atoms, an expected fact since the bridging bppz ligand is not planar but the monodentate pyridine is more or less perpendicular to the other two aromatic rings, precluding the spin exchange via the it ligand electrons.

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

 

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

 

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The fused heterocyclic compound represented in formula (1) has excellent effectiveness in pest control. (In the formula, A1 represents -NR4-, etc., A2 represents a nitrogen atom, etc., R1 represents an ethyl group, a cyclopropyl group, or a cyclopropylmethyl group, R2 represents -S(O)mR6 or -C(R7)(CF3)2, R4 represents a C1-C6 alkyl group optionally having one or more halogen atoms, R6 represents a C1-C6 haloalkyl group, R7 represents a fluorine atom or a chlorine atom, and m and n each represents 0, 1 or 2.)

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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 complexes of corroles have recently been a subject of keen interest due to their ligand non-innocent character and unique redox properties. Here we investigated bis-copper complex of a triply-linked corrole dimer that serves as a pair of divalent metal ligands but can be reduced to a pair of trivalent metal ligands. Reaction of triply-linked corrole dimer 2 with Cu(acac)2 (acac=acetylacetonate) gave bis-copper(II) complex 2Cu as a highly planar molecule with a mean-plane deviation value of 0.020 A, where the two copper ions were revealed to be divalent by ESR, SQUID, and XPS methods. Oxidation of 2Cu with two equivalents of AgBF4 gave complex 3Cu, which was characterized as a bis-copper(II) complex of a dicationic triply-linked corrole dimer not as the corresponding bis-copper(III) complex. In accord with this assignment, the structural parameters around the copper ions were revealed to be quite similar for 2Cu and 3Cu. Importantly, the magnetic spin?spin interaction differs depending on the redox-state of the ligand, being weak ferromagnetic in 2Cu and antiferromagnetic in 3Cu.

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

 

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The magnetic properties of chalcogenide spinel CuCr2Se4 nanocrystals have been studied as a function of crystallite size (15-30 nm). A solution-based method is used for the facile synthesis of the nanocrystals with good size control. They have close to cubic morphology with a narrow size distribution and exhibit superparamagnetic behavior at room temperature. The Curie temperature and saturation magnetization of the nanocrystals are lower as compared with the bulk and decrease with decreasing nanocrystal size. A similar trend is observed in the paramagnetic state for the Curie-Weiss temperature and effective magnetic moment. The low temperature magnetization behavior can be qualitatively explained by spin glass dynamics.

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

 

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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”