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The “one-pot” synthesis of 4-methyl-2-pentanone (methyl isobutyl ketone) from acetone over PdCu catalysts prepared from layered double hydroxides

Supported PdCu catalysts prepared from layered double hydroxides (LDHs) as precursors were evaluated in the gas phase reaction of acetone with hydrogen to methyl isobutyl ketone (MIBK). Two series of catalysts containing ca. 0.2 wt.% Pd and various amounts of Cu (Cu/Pd molar ratio of ca. 0.25, 0.5 and 1) were elaborated according to different methods. One series of precursors was obtained by impregnation of calcined Mg(Al)O mixed oxide with heterobinuclear Pdx Cu1-x acetylacetonates. A second series of precursors was synthesized by coprecipitation of Mg/Pd/Cu/Al LDHs. After calcination, both series were reduced at 473 K. The extends of basic, acid and metal functions were evaluated through microcalorimetric adsorption of CO2, TPD of NH3 and TPR of H2. It was found that the multifunctional transformation of acetone to MIBK was rate determined by the basic function. However, the way by which the catalysts were prepared, impregnation or coprecipitation, controls the extend of hydrogenated by-products, isopropyl alcohol and 4-methyl-2-pentanol. The extensive dilution by migrating MgAlOx species onto the metallic particles makes the coprecipitated catalysts highly selective by decreasing selectively the rate of C=O bond hydrogenation.

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

 

Brief introduction of Bis(acetylacetone)copper

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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”

 

Archives for Chemistry Experiments of Copper(I) oxide

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Copper(I) heteroleptic bis(NHC) and mixed NHC/phosphine complexes: Syntheses and catalytic activities in the one-pot sequential CuAAC reaction of aromatic amines

A series of 2-coordinate heteroleptic Cu(I) complexes of the general formula [Cu(IPr)(L)]PF6 (2-5, L = NHC or phosphine) have been synthesized via either (i) chlorido substitution by phosphine or in situ generated free NHC or (ii) the Ag-NHC transfer protocol using [CuCl(IPr)] (1) as a precursor (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene). The reactions of precursor 1 with diphosphine ligands afforded 3-coordinate heteroleptic Cu(I) complexes of the type [Cu(IPr)(L2)]PF6 (6 and 7, L2 = diphosphine). Complexes 1-7 have been subjected to a catalytic one-pot sequential CuAAC study, in which aromatic amines serve as the precursors to aryl azides. Hetero-bis(NHC) complexes 2-4 proved to be generally superior compared to their mixed NHC/phosphine counterparts 5-7. Overall, complex [Cu(Bn2-imy)(IPr)]PF6 (2), bearing the Bn 2-imy (Bn2-imy = 1,3-dibenzyl-imidazolin-2-ylidene) coligand, showed the best catalytic performance.

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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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Syntheses of 1,5-Benzothiazepines: Part III – Syntheses of 4-(p-Chlorophenyl)-2-(p-methoxyphenyl)-8-substituted-2,3-dihydro-1,5-benzothiazepines

4-Methoxy-4′-chlorobenzalacetophenone (IV) on reaction with 5-substituted 2-aminothiophenols (IIIa-f) in toluene gives 4-(p-chlorophenyl)-2-(p-methoxyphenyl)-8-substituted-2,3-dihydro-1,5-benzothiazepines (Va-f).Their structures have been established by IR, PMR and mass spectral data.

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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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Mechanochemical synthesis in copper(ii) halide/pyridine systems: Single crystal X-ray diffraction and IR spectroscopic studies

Whereas complexes of divalent metal halides (X = Cl, Br, I) with/from pyridine commonly crystallise as trans-[M(py)4X2] ¡¤2py, M on a site of 222 symmetry in space group Ccca, true for CuCl 2 and CuBr2 in particular, the copper(ii) iodide adduct is of the form [Cu(py)4I]I¡¤2py, Cu on a site of mm2 symmetry in space group Cmcm, and five-coordinate (square-pyramidal), the same cationic species also being found in 2[Cu(py)4I](I3)¡¤[(py) 2Cu(mu-I)2Cu(py)2] (structurally defined). Bromide or N-thiocyanate may be substituted for the unbound iodide ion in the solvated salt, resulting in complexes which crystallize in space group Ccca, but with both anions and the metal atom disordered. In [Cu(py)4(I 3)2], a pair of long Cu…I contacts approach a square-planar Cu(py)4 array. Assignments of the nu(CuN) and nu(CuX) (X = Br, I, SCN) bands in the far-IR spectra are made, the latter with the aid of analogous assignments for [Cu(py)2X2] (X = Cl, Br), which show a dependence of nu(CuX) on the Cu-X bond length that is very similar to that determined previously for copper(i) halide complexes. The structure of the adventitious complex [(trans-)(H2O)(py) 4CuClCu(py)4](I3)3¡¤H 2O is also recorded, with six- and five-coordinate copper atoms; rational synthesis provides [{Cu(py)4}2(mu-Cl)](I 3)3¡¤H2O with one water molecule less. In [{Cu(py)4Cl}(??)](I3)¡¤3py, square pyramidal [Cu(py)4Cl]+ cations, assisted by Cl…Cu interactions, stack to give rise to infinite polymeric strings. Several of these compounds were prepared mechanochemically, illustrating the applicability of this method to syntheses involving redox reactions as well as to complex syntheses involving up to five components. The totality of results demonstrates that the [CuII(py)4] entity can be stabilized in an unexpectedly diverse range of mononuclear and multinuclear complexes through the presence of lattice pyridine molecules, the bulky triiodide ion, or a combination of both.

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

 

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Laser induced electroactivity of polyamide composites

There were studied polyamide composites containing copper(II) oxide (CuO) and copper(II) acetoacetate Cu(acac)2, which after laser irradiation became fully prepared for an electroless metallization process. The composites were produced by use of typical processing methods such as extrusion and injection moulding. They were then irradiated with various numbers of ArF excimer laser pulses (lambda = 193 nm) at different fluences. The metallization procedure of the laser-irradiated samples was performed by use of a commercial metallization bath and formaldehyde as a reducing agent. The samples were examined using the FTIR and XPS techniques. Examinations were focused on elucidation of possible chemical reactions between CuO and Cu(acac)2, affected by both thermal processing and laser irradiation. It was found that CuO was efficiently reduced to Cu(0) and that surface became highly active for the direct electroless metallization. A chemical reaction model for this reduction is proposed as well.

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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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An insight into copper catalyzed allylation of alkyl zinc halides. Comparison of reactivity profiles for catalytic and stoichiometric alkylzinc-copper reagents

The gamma-selective allylation of catalytic and stoichiometric alkylzinc-cuprates have been kinetically studied. The reactivity profiles generated by allylation reactions of n-butylzinc chloride catalyzed by CuX compounds (X = I, Br, Cl, CN, SCN) and also catalyzed by n-butylzinc-copper reagents and di n-butylzinc-copper reagents were evaluated. Reactivity profiles for allylation of stoichiometric n-butylzinc-copper reagents and di n-butylzinc-copper reagents were also prepared. All CuX compounds have been screened for the preparation of Grignard reagent derived n-butylzinc-copper reagents and di n-butylzinc-copper reagents. The evaluation of the profiles indicates that the active catalyst might be RCu(X)ZnCl and also to some degree, R2CuZnCl ¡¤ ZnClX, which both could favor formation of gamma-product. All data supports the reductive elimination of sigma-allyl Cu (III) complex formed at vinylic terminal to give gamma-allylated product with a quite slow isomerization to sigma-allyl Cu (III) complex formed at allylic terminal to give alpha-allylated product. In the allylation mechanism of zinc cuprates, the role of counter ion, ZnCl+ has been discussed.

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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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Supramolecular helix-to-helix induction: A 3D anionic framework containing double-helical strands templated by cationic triple-stranded cluster helicates

(Figure Presented) All wrapped up: Supramolecular polymeric helices were fabricated by using cluster helicates as templates. The helicity of the template (see picture; gold spheres: Ni or Zn; blue spheres: O), upon hydrothermal treatment with CuSCN (gray spheres), is transferred to the strands of the resulting copper-based coordination polymer, which is wrapped around the helicate units in the final product.

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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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Construction of 1-2D CuI(or CuII) metal-organic architectures with metal thiocyanates and bipyridyl spacers: Syntheses, structures, and thermal properties

Three new coordination polymers based on IB metal thiocyanates, [CuII(NCS)2(DMSO)4(meso-dpb)]n (1), [Cu2II (NCS)4 (bpp)4]n (2), [CuI(NCS)(pia)]n (3) (dpb = 2,3-di(4-pyridyl)-2,3-butanediol, bpp = 1,3-bis(4-pyridyl)propane, pia = N,N?-(1,2-phenylene)diisonicotinamide), have been synthesized by the pre-assembly method and characterized by X-ray crystallography. In 1, CuII cations are bridged by meso-dpb ligands to form a one-dimensional (1D) linear chain. Compound 2 consists of 2D undulated layers of (4, 4) topology that show twofold parallel interpenetration. In the case of 3, the MI center adopts tetrahedral coordination geometry and the 2D networks are formed by organic ligand with “folding ruler-shaped” NCS–M chains. The thermal properties of 1-3 were also investigated.

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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”