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Copper-catalyzed cyanothiolation to incorporate a sulfur-substituted quaternary carbon center

Sulfur-containing nitriles have important research value in the life sciences due to their diverse biological activities resulting from the sulfur and cyano functional groups. Herein, a copper-catalyzed cyanothiolation of N-tosylhydrazones with thiocyanates to generate alpha-arylthioalkanenitriles bearing sulfur-substituted quaternary carbon center atoms has been described. This novel protocol involves the procedure of copper carbene species promoting S-CN bond cleavage and C-CN/C-S bond reconstruction to introduce both sulfur and cyano groups onto a single carbon center. This cyanothiolation reaction will greatly enhance the synthetic utility of carbenoid species as new entries for the construction of diverse heteroatom-containing nitriles via cyanofunctionalization of metal-carbene species.

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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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Studies on tris[thiocyanato-mu-thiocyanato-copper(I)] tris(pyridyl)molybdenum(III) and related complexes

Tetranuclear complexes of the type L3Mo[M(SCN)2]3 [M = Cu(I) or Ag(I); L = pyridine, nicotinamide or triphenylphosphine] have been prepared and characterised by elemental analyses, molar conductance,-magnetic moment, IR and electronic spectral studies. These studies reveal the presence of bridged and terminally S-bonded thiocyanates in the pyridine and nicotinamide complexes while bridged and terminally N-bonded thiocyanate groups were present in the triphenylphosphine complexes. Copper(I) and silver(I) are dicoordinated while molybdenum(III) is octahedral which has been supported by the HSAB principle.

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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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We¡¯ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 1111-67-7, and how the biochemistry of the body works.Formula: CCuNS

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The structural definition of adducts of stoichiometry MX:dppx (1:1) M = CuI, AgI, X = simple anion, dppx=Ph2P(CH 2)xPPh2, x = 3-6

Single crystal X-ray structural characterizations are recorded for a wide range of adducts of the form MX:dppx (1:1)(n), M = silver(I) (predominantly), copper(I), X = simple (pseudo-) halide or oxy-anion (the latter spanning, where accessible, perchlorate, nitrate, carboxylate – a range of increasing basicity), dppx=bis(diphenylphosphino)alkane, Ph2P(CH 2)xPPh2, x = 3-6. Adducts are defined of two binuclear forms: (i) [LM(mu-X)2L], with each ligand chelating a single metal atom, and (ii) [M(mu-X)2(mu-(P-L-P?)) 2M?] where both ligands L and halides bridge the two metal atoms; a few adducts are defined as polymers, the ligands connecting M(mu-X)2M? kernels, this motif persisting in all forms. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution (1H, 13C, 31P NMR, ESI MS) and in the solid state (IR).

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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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Process for producing 2,2,3-trimethylcyclopent-3-enecarbaldehyde (campholytic aldehyde)

A method for the production of campholytic aldehyde starting from campholenic aldehyde in the presence of a copper catalyst and a solvent,

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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 and crystal structures of multidimensional coordination polymers based on W/Cu/S clusters with flexible imidazole ligands

Reactions of [WES3]2- (E = S, O) with CuX (X = NCS, CN, I) in the presence of bix (bix = 1,4-bis(imidazole-1-ylmethyl)benzene) in DMF or CH3CN resulted in the formation of two novel 2D ? 3D interpenetrating coordination polymers [S2W2S 6Cu4(bix)2]n (1) and {[WS 4Cu4(NCS)2(bix)3]¡¤CH 3CN}n (2), a noninterpenetrating 3D polymer {[WS 4Cu2(bix)]¡¤DMF}n (3), and two 2D sheet polymers [WS4Cu3(CN)(bix)]n (4) and {[OWS 3Cu3(bix)2][I]¡¤DMF¡¤ 2H 2O}n (5), depending on the reaction temperature and the reagents used. Compound 1 contains a hexagonal prism of W2Cu 4S6 cluster core, which serves as a 4-connecting node to link equivalent nodes via bix ligands, forming a 2D (4,4) net. In 2, a WCu 4S4 core, which also acts as a 4-connecting node, connects the neighboring nodes either through single or double bix bridges, affording a different 2D (4,4) sheet. Inclined interpenetration occurs between two stacks of 2D sheets in the total structure of 1, while 2 involves a parallel interpenetration between the adjacent layers, both creating a 3D network. Compounds 1 and 2 represent the first examples of interpenetrating (4,4) frameworks with clusters as nodes and bidentate pyridyl-based ligands as linkers. Unlike 1 and 2, compound 3 has a noninterpenetrating 3D network, which is composed of the inorganic 1D (WS4Cu2)n chains linked by cis and trans bix ligands. Compound 4 features an inorganic 1D (WS4Cu3)n chain structure, which is linked by CN groups and bix ligands to form an infinite 2D network. Compound 5 is a 2D layer polymer with large inner cavities.

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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 Cuprous thiocyanate

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In-situ synchrotron far infrared spectroscopy of surface films on a copper electrode in aqueous solutions

Far infrared spectra of the surface films formed upon anodic oxidation of copper have been obtained in-situ for the first time in aqueous solution environments using a synchrotron source. The spectroelectrochemical behavior of copper was studied in NaOH and in a dilute solution of KSCN in perchlorate. The oxide film at -0.05 V vs. SCE in 0.1 M NaOH solution has been identified as Cu2O. In the passive region at 0.3 V, CuO and Cu(OH)2 appear to be present on the surface. Vibrational bands observed in 0.025 M KSCN + perchlorate solution are attributed to a multilayer film of copper(I) thiocyanate.

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

 

New explortion of 1317-39-1

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Beta-lactams and their production

A beta-lactam compound of the formula: STR1 wherein R1 and R2 are, the same or different, each a hydrogen atom or a lower alkyl group, R30 is a hydroen atom or a lower alkyl group having a beta-configuration, R4 is a carboxyl-protecting group, X is a hydrogen atom or a protected hydroxyl group and COZ is a protected thiolcarboxyl group, which is useful as a valuable intermediate in the stereospecific production of 1-alkylcarbapenem compounds.

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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 supramolecular CuCN complexes by decomposing CuSCN: A general route to CuCN coordination polymers?

The solvothermal reaction of CuSCN with 1,2-bis(diphenylphosphino)ethane (dppe) yielded a coordination polymer, which was characterized to be a complex of CuCN and 1,2-bis(diphenylthiophosphinyl)ethane (dppeS2): [(CuCN)2(dppeS2)]n (1). The identification of complex 1 reveals that CuSCN was decomposed and the sulfur was transferred to dppe, and represents a new example of the transformation of inorganic sulfur to organic sulfur. The weak coordination interactions between CuCN and dppeS 2 indicate that dppeS2 may be substituted by ligands with strong coordination ability. The ligand 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tpt) was chosen as a substitute ligand. Three novel CuCN coordination polymers of tpt were synthesized and characterized: [Cu2(CN) 2(tpt)]n (2) with a 3-D (10,3)-a network, [Cu 2(CN)2(tpt)]n (3) and [Cu2(SCN)(CN) (tpt)]n (4) both with a 2-D (6,3) network, and only complex 2 can be obtained from CuCN directly. Interestingly, compounds 2 and 3 are genuine high-dimensional supramolecular isomers. During the syntheses of 2-4, single crystals of dppeS2 were isolated, which indicates it was substituted by tpt ligand and also confirmed the transformation of sulfur from CuSCN to dppe. The transformation of sulfur can be observed only when the temperature is relative high (>160 C). At 140 C, complex 5 containing only CuSCN was attained and no dppeS2 has been monitored in the resulting filtrate. The Royal Society of Chemistry 2006.

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

 

Brief introduction of 1111-67-7

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Luminescent CuI thiocyanate complexes based on tris(2-pyridyl)phosphine and its oxide: from mono-, di- and trinuclear species to coordination polymers

Tris(2-pyridyl)phosphine oxide reacts with CuSCN to form a variety of luminescent complexes, depending on the specified metal-to-ligand ratio and the solvent used, viz. mononuclear [Cu(N,N?,N??-Py3P=O)(NCS)], dinuclear (N,N?-Py3P=O)Cu(SCNNCS)Cu[(N,N?-Py3P=O)], their co-crystal (2?:?1, correspondingly) and trinuclear {Cu(NCS)[SCNCu(N,N?,N??-Py3P=O)]2}. In the solid state, these complexes feature red-orange emission upon UV photoexcitation. The reaction of tris(2-pyridyl)phosphine with CuSCN quantitatively produces an almost insoluble coordination polymer, [Cu(Py3P)NCS]n, which exhibits bright green emission. The synthesized compounds are the first members of the hitherto unknown family of Cu(i) thiocyanate complexes supported by tripodal ligands.

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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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High-Efficiency Fullerene Solar Cells Enabled by a Spontaneously Formed Mesostructured CuSCN-Nanowire Heterointerface

Fullerenes and their derivatives are widely used as electron acceptors in bulk-heterojunction organic solar cells as they combine high electron mobility with good solubility and miscibility with relevant semiconducting polymers. However, studies on the use of fullerenes as the sole photogeneration and charge-carrier material are scarce. Here, a new type of solution-processed small-molecule solar cell based on the two most commonly used methanofullerenes, namely [6,6]-phenyl-C61-butyric acid methyl ester (PC60BM) and [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM), as the light absorbing materials, is reported. First, it is shown that both fullerene derivatives exhibit excellent ambipolar charge transport with balanced hole and electron mobilities. When the two derivatives are spin-coated over the wide bandgap p-type semiconductor copper (I) thiocyanate (CuSCN), cells with power conversion efficiency (PCE) of ?1%, are obtained. Blending the CuSCN with PC70BM is shown to increase the performance further yielding cells with an open-circuit voltage of ?0.93 V and a PCE of 5.4%. Microstructural analysis reveals that the key to this success is the spontaneous formation of a unique mesostructured p?n-like heterointerface between CuSCN and PC70BM. The findings pave the way to an exciting new class of single photoactive material based solar cells.

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