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Total synthesis of apicularen a through transannular pyran formation

A macrocyclization-transannulation strategy is the crux of an efficient total synthesis of the benzolactone enamide apicularen A (see scheme; Bn = benzyl). Key steps include a four-component coupling, a Stille cross-coupling to introduce the aromatic moiety, and the formation of the enamide from a hemiaminal. The size-selective macrolactonization of the ethoxyvinyl ester shown was followed by transannular etherification in excellent yield.

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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 structural characterization of six pentanuclear and tetranuclear Mo/W-Cu-S clusters with BIS(Diphenylphosphanyl) methane

Six heterothiometalic clusters, namely,[WS4Cu4(dppm)4]-(ClO4)2?2DMF?MeCN (1), [MoS4Cu4(dppm)4](NO3)2?MeCN (2) [MoS4Cu3(dppm)3](ClO4)?4H2O (3), [WS4Cu3(dppm)3](NO3)?4H2O (4), [WS4Cu3(dppm)3]SCN?CH2Cl2 (5), and [WS4Cu3(dppm)3]I?CH2Cl2 (6) [dppm = bis (diphenylphosphanyl)methane] were synthesized. Compounds 1?4 were obtained by the reactions of (NH4)2MS4 (M = Mo, W) with [Cu2(mu2-dppm)2(MeCN)2(ClO4)2] {or [Cu(dppm)(NO3)]2} in the presence of 1,10-phen in mixed solvent (CH3CN/CH2Cl2/DMF for 1 and 2, CH2Cl2/CH3OH/DMF for 3 and 4. Compounds 5 and 6 were obtained by one-pot reactions of (NH4)2WS4 with dppm and CuSCN (or CuI) in CH2Cl2/CH3OH. These clusters were characterized by single-crystal X-ray diffraction as well as IR,1H NMR, and31P NMR spectroscopy. Structure analysis showed that compounds 1 and 2 are ?saddle-shaped? pentanuclear cationic clusters, whereas compounds 3?6 are ?flywheel-shaped? tetranuclear cationic clusters. In 1 and 2, the MS42- unit (M = W, Mo) is coordinated by four copper atoms, which are further bridged by four dppm molecules. In compounds 3?6, the MS42- unit is coordinated by three copper atoms and each copper atom is bridged by three dppm 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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Dehydroxylative Trifluoromethylthiolation, Trifluoromethylation, and Difluoromethylation of Alcohols

CF3S, CF3 and HCF2 groups have been identified as valuable functionalities for drug development. Despite significant accomplishments in the trifluoromethylthiolation, trifluoromethylation and difluoromethylation reactions, directly converting common functional groups into CF3S, CF3 or HCF2 groups is still highly desirable. Described here is the dehydroxylative trifluoromethylthiolation, trifluoromethylation and difluoromethylation of alcohols promoted by a R3P/ICH2CH2I system. All of these dehydroxylative reactions were achieved under mild conditions via the activation of the hydroxyl group by the R3P/ICH2CH2I system. A wide substrate scope and good functional group tolerance were observed.

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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(I) pseudohalide complexes with 4,6-dimethylpyrimidine-2(1H)-thione and triphenylphosphane as ligands. The X-ray crystal structures of [Cu(N3)(dmpymtH)(PPh3)2] and [Cu(NCS)(dmpymtH)(PPh3)2]

The preparation of mixed-ligand copper (I) coordination compounds containing pseudohalides (azide and thiocyanate), 4,6-dimethylpyrimidine-2(1H)-thione (dmpymtH), and triphenylphosphane is described. The crystalline and molecular structure of [Cu(N3)(dmpymth)(PPh3)2] (2) and [Cu(NCS)(dmpymtH)(PPh3)]2 (3) have been determined by X-ray diffraction methods. The copper atom has a tetra-coordinate CuNP2S chromophore with distorted tetrahedral coordination in both complexes. Vibrational and 1H, 13C, 31P NMR spectra of the complexes are discussed and related to the structures

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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(II)-mediated oxime-nitrile coupling in non-aqueous solutions: Synthetic, structural and magnetic studies of the copper(II)-salicylaldehyde oxime reaction system

The reactions of salicylaldehyde oxime (H2salox) with Cu II precursors yielded the known complexes [Cu(Hsalox)2] (1) and [Cu(Hsalox)2]n (2), as well as complexes [Cu 3(salox)(L1)(L2)]¡¤MeCN (3¡¤MeCN), [CuCl(L1)] (4) and [Cu2Na(O2CMe) 5(HO2CMe)]n (5), where L1 – = o-O-C6H4-CHNO-C(CH3)NH and L23- = o-O-C6H4-CHNO-C(o-O-C 6H4)N. L1- was formed in situ via the nucleophilic addition of the oximato O-atom of salox2- to the unsaturated nitrile group of the MeCN reaction solvent. L2 3- is also formed in situ probably through the nucleophilic attack of the oximato O-atom to the unsaturated nitrile group of salicylnitrile; the latter, although not directly added to the reaction mixture, can be produced via the dehydration of salox2-. Compounds 1 and 2 contain Hsalox – bound to the metal center in two different coordination modes; they both contain the same mononuclear unit, however a 2D network is generated in 2 due to a relatively long Cu-Ooximato bond. Compound 3 contains three different ligands, i.e. salox2-, L1- and L 23-, which act as mu3-kappa2O: kappaO?:kappaN, kappaO:kappaN:kappaN? and mu3-kappa2O:kappa2N:kappaO?: kappaN?, respectively, whereas 4 consists of a square planar Cu II atom bound to a kappaO:kappaN:kappaN? L 1- and a chloride ion. Compound 5 consists of dinuclear [Cu2(O2CMe)5(HO2CMe)]- units and Na+ ions assembled into an overall 3D network structure. Magnetic susceptibility measurements from polycrystalline samples of 2 and 5 gave best-fit parameters J = +0.36 cm-1 (H = -JS? iS?j) and J = -360 cm-1, zj = +20 cm -1 (H = -JS?iS?j – zJ?S z?S?z), 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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Assembly of chiral two- and three-dimensional copper(I) pseudohalide based coordination polymers with asymmetrically substituted pyrazine and pyrimidine ligands

The coordination polymers 2?[(CuCN)2(mu-2 Mepyz)], 3?[CuCN(mu-2 Mepyz)] and 3?[CuCN(mu-4 Mepym)] (1-3) (2 Mepyz = 2-methylpyrazine; 4 Mepym = 4-methylpyrimidine) may be prepared by self-assembly in acetonitrile solution at 100 C (1, 3) or without solvent at 20 C (2). All three contain 1?[CuCN] chains that are bridged by the bidentate aromatic ligands into sheets in 1 and 3 D frameworks in 2 and 3. Reaction of CuSCN with these heterocyclic diazines at 100 C leads to formation of the lamellar coordination polymers 2?[(CuSCN)(mu-2 Mepyz)] (4) and 2?[CuSCN ¡¤ (4 Mepym-kappaN1)] (5), which contain respectively 1?[CuSCN] chains and trans-trans fused 2?[CuSCN] sheets as substructures. The presence of an asymmetric substitution pattern in 2 Mepyz and 4 Mepym induces the adoption of a chiral structure by 2 and 5 (space groups P212121 and P1).

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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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Versatility of the nature of the magnetic Cu(II)-U(IV) interaction. Syntheses, crystal structures and magnetic properties of Cu2U and CuU compounds

Treatment of [M(H2Li)] with U(acac)4 in refluxing pyridine led to the formation of the trinuclear complexes [{MLi(py)x}2U] [L1 = N,N?-bis(3-hydroxysalicylidene)-2,2-dimethyl-1,3-propanediamine and M = Ni, Cu or Zn; L2 = N,N?-bis(3-hydroxysalicylidene)-1,3-propanediamine and M = Cu or Zn; L3 = N,N?-bis(3-hydroxysalicylidene)-2-methyl-1,2-propanediamine and M = Ni, Cu or Zn; x = 0 or 1]. The dinuclear compounds [ML3(py)U(acac)2] (M = Cu, Zn) were isolated from the reaction of [M(H2L3)] and U(acac)4 in pyridine at 60C. The crystal structures of the trinuclear complexes are built up by two orthogonal MLi(py)x units which are linked to the central uranium ion by the two pairs of oxygen atoms of the Schiff base ligand; the U(IV) ion is found in the same dodecahedral configuration but the Cu(II) ion coordination geometry and the Cu … U distance are different by passing from L1 or L2 to L3, due to the shortening of the diimino chain of L3. These geometrical parameters seem to have a great influence on the magnetic behaviour of the complexes since the Cu-U coupling in [{CuLi(py)x}2U] (i = 1, 2) is ferromagnetic while it is antiferromagnetic in [{CuL3(py)x}2U]. In the compounds [{CuL3(py)x}2U] and [CuL3(py)U(acac)2], the Cu coordination and the Cu … U distance are very similar, and both exhibit an antiferromagnetic interaction.

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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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Enantioselective Organocatalyzed Direct alpha-Thiocyanation of Cyclic beta-Ketoesters by N -Thiocyanatophthalimide

A new electrophilic thiocyanation reagent, N-thiocyanatophthalimide, was synthesized and applied to the first example of catalytic asymmetric electrophilic alpha-thiocyanation of various cyclic beta-ketoesters by the bifunctional cinchona alkaloid catalysis. Thus, a variety of chiral alpha-thiocyanato beta-ketoesters with a quaternary carbon center have been achieved in excellent yields (up to 99%) and high enantioselectivities (up to 94% ee) in a convenient manner.

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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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Balancing electrical and optical losses for efficient 4-terminal Si-perovskite solar cells with solution processed percolation electrodes

The unprecedented rise in efficiency of perovskite-based photovoltaics has sparked interest in semi-transparent devices, particularly for tandem structures. Despite promising reports regarding efficiency and reduced parasitic absorption, many devices still rely on processes from the gas phase, compromising both applicability and cost factors. Here, we report all-solution perovskite solar cells with improved infrared transparency ideally suited as top-cells for efficient multi-junction device configurations. We demonstrate the functionality of copper(i) thiocyanate as antireflective layer and as selective contact between the transparent conductive oxide and the perovskite. This concept allows us to fabricate an opaque device with steady state efficiency as high as 20.1%. By employing silver nanowires with robust environmental stability as the bottom electrode, we demonstrate different regimes of device performance that can be described through a classical percolation model, leading to semi-transparent solar cells with efficiencies of up to 17.1%. In conjunction with the implementation of an infrared-tuned transparent conductive oxide contact deposited on UV-fused silica, we show a full device average transmittance surpassing 84% between 800 and 1100 nm (as opposed to 77% with PEDOT:PSS as the selective contact). Finally, we mechanically stacked optimized perovskite devices on top of high performing PERL and IBC silicon architectures. The measured imputed output efficiency of the 4-terminal perovskite-silicon solar cell was 26.7% and 25.2% for the PERL-perovskite and IBC-perovskite, 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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One-pot’ synthesis of two molybdenum/tungsten (VI)-copper(I) mixed metal clusters under catalysis of 1,10-phenathroline

Under the catalysis of 1,10-phenathroline (phen), (NH4) 2 M’S4 (M’ = Mo,W) reacts with CuSCN and dppm in mixed solvent MeCN/DMF (1:1) to yield two saddle-shaped clusters [WS 4Cu4(SCN)2 (dppm)3] ?3DMF?2CH3CN (1) and [MoS4Cu4(SCN) 2 (dppm)3]?4DMF (2) (dppm = bis (diphenylphosphino) methane). Compounds 1-2 were characterized by elemental analysis, IR, UV-Vis, 1H NMR, 31P NMR, and single-crystal X-ray diffraction. Each [M’S4]2- (M’ = Mo, W) anion coordinates to four Cu atoms through four bridging S atoms, and all S atoms are coordinated with two Cu atoms. In each cluster the four Cu atoms are almost in one plane, and the M’ atom is above the plane. Cluster 1 was characterized by luminescent with the lambdaem = 545 nm. The possible catalysis mechanism of phenathroline is discussed.

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