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The synthesis of aromatic dicarboxaldehydes is described along with their reactivity in the [3 + 3] cyclocondensation reaction with (1R,2A)- diaminocyclohexane to give trianglimine macrocycles. In particular, the scope and limitation of the reaction with regard to complete control of the cavity size of the macrocycles is discussed producing a total of 11 macrocycles with different cavity sizes ranging from 9 to 23 A. The Royal Society of Chemistry 2005.

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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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X-Ray structural and EPR spectroscopic studies of the redox-related pairs [WX(CO)(MeC=CMe)Tp’](z) (X = F, Cl, Br and I; z = 0 and 1) [Tp’ = hydrotris(3,5-dimethylpyrazolyl)borate] are consistent with the HOMO of the d4 (z = 0) species being pi-bonding with respect to the W-CO bond, pi- antibonding with respect to the W-X bond, and delta-bonding with respect to the W-alkyne bond.

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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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In electrochemical systems imperfect thermostating inevitably leads to the presence of bulk convective flows. As recognised by Nernst [Z. Phys. Chem., 1904, 52] damping of these bulk convective flows next to a solid surface, or at the electrode, leads to diffusional mass transport predominating locally. This work questions the exclusivity of diffusional transport and provides hitherto unexplored physical insights into how thermally induced flows in bulk solution can, on both macro- and microelectrodes, influence a voltammetric measurement. Imperfect thermostating results in flows in the bulk solution which are predicted and here expeimentally shown to be of the order of 100 mum s-1. Here we show that even in the absence of natural convective flows induced by the electrochemical reaction itself, this thermally induced bulk convection can significantly affect the voltammetric response. First, evaporative losses from an open electrochemical cell can be sufficient to produce convective flows that can alter the electrochemical response. Second, electrodes with various sizes and geometries have been investigated and experimental results evidence that the sensitivity of an electrode to these flows in bulk solution is to a large extent controlled by the size of the surrounding non-conductive supporting substrate used to insulate parts of the electrode.

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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 facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt3)4 (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt 3)4, but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Bronsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.

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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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Xenopus oocytes were used as cellular and molecular sentinels to assess the effects of a new class of organometallic compounds called ferrocenyl dihydroquinolines that have been developed as potential anti-cancer agents. One ferrocenyl dihydroquinoline compound exerted deleterious effects on oocyte survival after 48 h of incubation at 100 muM. Two ferrocenyl dihydroquinoline compounds had an inhibitory effect on the resumption of progesterone induced oocyte meiosis, compared to controls without ferrocenyl groups. In these inhibited oocytes, no MPF (Cdk1/cyclin B) activity was detected by western blot analysis as shown by the lack of phosphorylation of histone H3. The dephosphorylation of the inhibitory Y15 residue of Cdk1occurred but cyclin B was degraded. Moreover, two apoptotic death markers, the active caspase 3 and the phosphorylated histone H2, were detected. Only 7-chloro-1-ferrocenylmethyl-4-(phenylylimino)-1,4-dihydroquinoline (8) did not show any toxicity and allowed the assembly of a histologically normal metaphase II meiotic spindle while inhibiting the proliferation of cancer cell lines with a low IC50, suggesting that this compound appears suitable as an antimitotic agent.

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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

 

Brief introduction of 1,1′-Dibenzoylferrocene

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The structure of protonated ferrocenes has been investigated using 1H NMR and 57Fe Moessbauer spectroscopy.The ketones were fully protonated in CF3CO2H and in 70percent H2SO4/H2O.In more concentrated sulphuric acid < > 90percent H2SO4/H2O) rapid heteroannular sulphonation occurred.No evidence was obtained of any iron protonation in these systems.For the para substituted aromatic derivatives C5H5FeC5H4COC6H4X the NMR data indicates steric inhibition to resonance. 1,1′-Diketones are doubly protonated in strongly acid media (98percent H2SO4, CF3SO3H).Moessbauer data on the solid ketones showed decrease in quadrupole splitting (QS), relative to ferrocene itself, of about 0.12 mm s-1 for each successive acyl function added.For solid solutions of the protonated ketones in CF3CO2H this decrease (DeltaQS) was much larger at about 0.28 mm s-1.The results are interpreted as involving electron withdrawal from ring-based orbitals (epsilon1), rather than the iron-based orbitals (epsilon2).In the aromatic series, DeltaQS was significantly smaller for electron withdrawing substituents.

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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

 

Discover the magic of the Ferrocenemethanol

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SDS of cas: 1273-86-5, Healthcare careers for chemists are once again largely based in laboratories, although increasingly there is opportunity to work at the point of care, helping with patient investigation. 1273-86-5, Name is Ferrocenemethanol, molecular weight is 206.99. molecular formula is C11H3FeO. In an Review,once mentioned of 1273-86-5

This review provides an update on the research conducted on the fabrication and utilization of hypoxanthine (Hx) biosensors published over the past four decades. In particular, the review focuses on progress made in the development and use of Hx biosensors for the assessment of fish and meat quality which has dominated research in this area. The various fish and meat freshness indexes that have been proposed over this period are highlighted. Furthermore, recent developments and future advances in the use of screen-printed electrodes and nanomaterials for achieving improved performances for the reliable determination of Hx in fish and meat are discussed.

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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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We report the synthesis of trifluoromethylated metallocenes (M=Fe, Ru) and related metal-free compounds for comparison of their biological properties with the aim to establish structure-activity relationships toward the anti-proliferative activity of this compound class. All new compounds were comprehensively characterized by NMR spectroscopy (1H, 13C, 19F), mass spectrometry, IR spectroscopy, and elemental analysis. A single-crystal X-ray structure was obtained on the Ru derivative, 1-(1-hydroxy-1-hexafluoromethylethyl)ruthenocene (3). The cytotoxicity of all compounds was tested on MCF-7, HT-29, and PT-45 cells, and IC50 values as low as 12 muM were observed. Both the metallocene moiety and the hydroxy function are crucial for cytotoxicity. In addition, the activity decreased sharply even if only one trifluoromethyl group was replaced with a methyl group. Electrochemical investigations by cyclic voltammetry revealed that all CF3-containing compounds are harder to oxidize than the unsubstituted metallocenes. Moreover, log-P determination by RP-HPLC showed the fluorinated derivatives to have higher lipophilicity, with log-P values up to 4.6. At the same time, the generation of reactive oxygen species (ROS) in Jurkat cells by these compounds was investigated by flow cytometry. Strong ROS production was shown exclusively for the bis-CF3 derivative 1-(1-hydroxy-1-hexafluoromethylethyl)ferrocene (1) after 6 and 24 h. Also on the Jurkat cell line, only compound 1 strongly induces necrosis after 24 and 48 h, as shown by annexin V/propidium iodide staining. No induction of apoptosis was observed. We propose that compound 1 is more efficiently incorporated into cancer cells relative to all other derivatives, causing significant induction of oxidative stress within the cell, which ultimately leads to cell death. Fluorinated oxidizers: A series of trifluoromethyl-containing metallocenes was synthesized to carry out SAR determinations. All compounds were tested for cytotoxic effects against a range of cancer cell lines, ROS production, electrochemical behavior, lipophilicity, and their capacity to induce apoptosis/ necrosis. Cytotoxicity assays underscore the crucial role of the metallocene moiety, CF3 groups, and the OH function for anti-proliferative effects.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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A short and efficient preparation of conjugated oligo(phenylene-ethylene) thiols bearing redox-active ferrocene moieties is described. While minimising the number of synthetic steps, the proposed strategy permits the development of sets of oligomers with varying chain length. The redox properties of the compounds in solution are determined. Preliminary studies of self-assembled monolayers (SAMs) on gold electrodes are discussed, and indicate that electron transfer through the SAMs is indeed rapid. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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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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In this paper we present preliminary electrochemical investigations into the transport properties of free standing ultra-thin surfactant films and the associated meniscus. We describe a new electrochemical cell composed of a 25 mum diameter gold wire placed through a stable surfactant film which served as the electrolyte. Solutions containing anionic sodium dodecyl sulphate (SDS) or non-ionic Triton-X100 surfactants, with background electrolyte NaCl and with electroactive probe ferrocyanide or ferrocene methanol, were used to create the surfactant films. The electrolyte was an ultra-thin surfactant film creating a two dimensional solution with a thickness between 300 and 1000 nm, and its meniscus at the gold wire, within which the electroactive probe was free to diffuse. Cyclic voltammetry was used to oxidise and reduce the electroactive probe within the surfactant film and meniscus. It was shown that films and the associated meniscus formed from SDS solution almost completely excluded negatively charged ferrocyanide. A finite difference simulation showed that the voltammetry was dominated by the meniscus region, the unusual spatially-varying bounded geometry of which resulted in an unusual dependence on potential scan rate of the peak to peak separation (decreasing with increasing scan rate) and anodic:cathodic peak current ratio (increasing with increasing scan rate).

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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