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The discovery of novel drugs against animal parasites is in high demand due to drug-resistance problems encountered around the world. Herein, the synthesis and characterization of 27 organic and organometallic derivatives of the recently launched nematocidal drug monepantel (Zolvix) are described. The compounds were isolated as racemates and were characterized by1H,13C, and19F NMR spectroscopy, mass spectrometry, and IR spectroscopy, and their purity was verified by microanalysis. The molecular structures of nine compounds were confirmed by X-ray crystallography. The anthelmintic activity of the newly designed analogues was evaluated in vitro against the economically important parasites Haemonchus contortus and Trichostrongylus colubriformis. Moderate nematocidal activity was observed for nine of the 27 compounds. Three compounds were confirmed as potentiators of a known monepantel target, the ACR-23 ion channel. Production of reactive oxygen species may confer secondary activity to the organometallic analogues. Two compounds, namely, an organic precursor (3 a) and a cymantrene analogue (9 a), showed activities against microfilariae of Dirofilaria immitis in the low microgram per milliliter range.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Amphiphilic polymers have attracted extensive research attention in constructing various nanostructures by self-assembly. Here we designed and synthesized two amphiphilic bimetallic polymers with different length of the tails P1 and P2, in which Fe,Pt-containing conjugated complex acted as the hydrophobic block and hydrophilic poly(ethylene glycol)(PEG)was bonded to the bimetallic core as the flexible tails. P1 and P2 were used as the single-source precursors to prepare FePt nanoparticles (NPs)by one-pot pyrolysis. The resultant NPs were fully characterized and had a chemically ordered face-centered tetragonal (fct)phase with high crystallinity. The size of NPs pyrolyzed from P1 and P2 was 24.7 and 8.2 nm with the relative coercivity of 9.6 and 1.3 kOe, respectively. The difference was preliminarily explained by the discrepancy of their degrees of crystallinity, and also analyzed by the precursors? structural effect. The amphiphilic design showed a good potential in preparing monodisperse ferromagnetic FePt NPs, and the possible favorable properties of self-assembly might provide a bright venue for future magnetic recording media.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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By using an oxidizing directing group, a mild, efficient Rh(III) catalyzed C-H olefination reaction between N-phenoxyacetamides and alkenes was developed. This reaction provided a straightforward way for the synthesis of ortho-alkenyl phenols, and the directing group is traceless in the product.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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A novel asymmetric 1,1?-ferrocene-derived Schiff base ligand has been prepared by the condensation reaction of 1,1?-diacetylferrocene with 2-aminopyridine and 2-aminothiazole. Its transition metal complexes of the type [M(L)]Cl2 and [M(L)(Cl2)] [M = Cu(II),Co(II) and Ni(II)] have been prepared and characterized by their physical, analytical and spectral data. The Cu(II) complex shows square-planar whereas the Co(II), Ni(II) and Zn(II) complexes show octahedral geometry.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The prevalence of solvent effects in heterogeneous catalysis in condensed media has motivated developing theoretical assessments of solvent structures and their interactions with reaction intermediates and transition states. Computed Properties of C14H6FeO2, You can get involved in discussing the latest developments in this exciting area about 1273-94-5

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Thiomethoxychalcone-based ligands bis[3,3-bis(methylsulfanyl)]-1,1?- eta5-ferrocenyl-2-propen-1-one (L1), 3,3-bis(methylsulfanyl)-1-eta5-ferrocenyl-2-propen-1-one (L 2), and 3-methylsulfanyl-3-sulfanyl-1-eta5-ferrocenyl-2- propen-1-one (L3) have been synthesized on the ferrocene backbone by varying the number of chalcone arms and thiomethoxy substitutents. The single-crystal X-ray crystallographic analyses of all three ligands are reported in which crystals of L1 were obtained as both syn and anti conformers and showed the conformational freedom of the two cyclopentadienyl (Cp) units. L1-L3 are studied extensively toward their applicability in the colorimetric sensing of metal ions in solution. The solution-state study of mono- and bis(thiomethoxy)ferrocenylchalcone- functionalized ligands L1 and L2 showed selective colorimetric sensing for Hg2+ over Li+, Na+, Ca2+, Mg2+, Cr2+, Mn2+, Fe 2+, Co2+, Ni2+, Cu2+, Zn 2+, Cd2+, and Au3+ in acetonitrile. In both cases, a selective color change from orange to purple was observed with Hg 2+ and the resultant solution showed the appearance of a new peak at 565 nm (epsilon = 3920 M-1 cm-1) for L1 and 600 nm (epsilon = 1140 M-1 cm-1) for L2 in the UV/vis experiments. The UV/vis titration profiles of L1 and L 2 indicate the formation of 2:1 (L1/Hg2+) and 1:1 (L2/Hg2+) initial complexations in solution. On the other hand, L3 with thiomethoxy- and thiol-functionalized ferrocenylchalcone showed no appreciable color change with Hg2+ under the same experimental conditions. Attempts were made to isolate single crystals of the resulting purple solution obtained in the cases of L1 and L2 with Hg2+. In both cases, crystals suitable for a single-crystal X-ray diffraction study were isolated in very low yield by a layer diffusion technique. The single-crystal structural investigations demonstrated the formation of a sulfide-encapsulated mercury thiolate cuboctahedron cluster, [Hg8S(SCH3)12] 2+, upon a selective chemodosimetric desulfurization reaction between Hg2+ and L1 or L2. Cyclic voltammetric studies also support the Hg2+-induced cleavage of thiomethoxy groups.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Ferrocene grafted siloxanes were prepared in high yields (?79-97%) via Rh-catalyzed dehydrogenative coupling of a series of monomeric, polymeric, and cyclic hydrosiloxanes with ferrocenemethanol. Wilkinson’s catalyst was the most efficient of those surveyed (Karstedt’s catalyst, H2PtCl6, Co2 (CO)8, 10% Pd/C, 10% Pt/C, 5% Rh/C) with respect to yield and selectivity. Benzene and toluene were better solvents than tetrahydrofuran and methylene chloride.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Redox recycling systems enable marked improvement of electrochemical detection capabilities. Enhanced sensitivity is achieved by employing a sacrificial redox species that recycles the analyte back to its original oxidation state through a catalytic homogeneous electron transfer. Repetition of the cycle leads to multiple heterogeneous electron transfer events for each analyte molecule, serving to enhance the transduced signal. The success of redox recycling is intimately linked to the selectivity of heterogeneous electron transfer: the analyte should undergo a fast reaction while the sacrificial species should ideally be excluded from contributing directly to the current. This requirement stems from the relationship between selectivity and detection limit in that the direct heterogeneous electrolysis of the sacrificial additive can increase the background current which can degrade detection capabilities. Earlier work has shown that electrodes with suitable selectivity can be constructed using alkanethiolate monomolecular films on gold, with various ferrocenes (FcX) serving as a model analyte and ferrocyanide (Fe (CN)64 -) acting as the recycling agent [A.J. Bergren, M.D. Porter, J. Electroanal. Chem. 585 (2005) 172, A.J. Bergren, M.D. Porter, J. Electroanal. Chem. 591 (2006) 189, P.T. Radford, M. French, S. E. Creager, Anal. Chem. 71 (1999) 5101, P.T. Radford, S.E. Creager, Anal. Chim. Acta 449 (2001) 199, S.E. Creager, P.T. Radford, J. Electroanal. Chem. 500 (2001) 21]. The work herein investigates the origins of the selectivity for this system by analysis of the different pathways (e.g., electron transfer kinetics, size-exclusion, and partitioning) that can suppress the heterogeneous electrolysis of Fe (CN)64 -, while maintaining that for FcX at a rapid level. Comparisons of experimental data to expectations derived from model assessments are used to evaluate the relative importance of each possibility. The properties (i.e., size and hydrophobicity) of several FcX molecules and Fe (CN)64 – are also examined to provide additional insight into the processes that are important in creating a potent redox recycling system. These results show how the inherent differences in the heterogeneous electron transfer reaction rates can dictate the kinetic selectivity of the system. These findings indicate that partitioning augments the kinetic selection for the FcX / Fe (CN)64 – system, leading to the high level of observed selectivity.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Copper-promoted azide-alkyne cycloadditions were attempted to synthesize a series of variedly functionalized 1H-1,2,3-triazole-linked isatin-ferrocene, ferrocenylmethoxy-isatin and isatin-ferrocenyl-chalcone conjugates. The synthesized scaffolds were assayed for their inhibitory activity against T. vaginalis as well as several common normal human flora bacteria. The observed inhibitory activities against T. vaginalis and undetectable inhibition of microflora bacteria suggest that these compounds may be specific against trichomonad protozoa and could serve as a new scaffold for synthesis of novel compounds against this important human pathogen.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Dehydrogenative borylation of alkenes and 1,3-dienes was realized by carrying out the reaction in the presence of bis(pinacolato)diboron (B2pin2) and a catalytic amount of PSiP-pincer palladium complex. This protocol has the following notable features. 1) Monoanionic nature of the PSiP-pincer ligand prevents the formation of boryl(hydrido)- or dihydridopalladium species, enabling synthesis of various vinyl- or dienylboronic esters in good yield from a 1:1 mixture of B2pin2 and alkenes or 1,3-dienes without forming hydroboration or hydrogenation products. 2) Due to the strong trans influence of the silicon atom, PSiP-pincer palladium complex showed high activity toward migratory insertion. 3) Suppression of these side-reactions and the high reactivity of the PSiP-pincer palladium complex enabled an efficient, successive dehydrogenative borylation to give 1,1- or 1,2-diborylated products depending on the kind of substituent on alkenes by using more than 2 equivalents of B2pin 2. Mechanistic study revealed that PSiP-pincer borylpalladium complex was generated from hydridopalladium complex and B2pin2, and this complex underwent alkene insertion followed by beta;- hydride elimination to give alkenylboronic ester with regeneration of the hydridopalladium complex.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Reaction of [IrCp?Cl2]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6H4) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp?,RIr?. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc,Sp,RIr. Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion