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Cyclic azomethine imines possessing a beta-aminocarbonyl motif are accessed from simple alkene and hydrazone starting materials. A thermal, concerted alkene aminocarbonylation pathway involving an imino-isocyanate intermediate is proposed and supported by DFT calculations. A notable feature of the process is the steric shielding present in the dipoles formed, which allows for facile purification of the products by chromatography or crystallization. In addition, a fluorenone-derived reagent is reported, which provides reactivity with several alkene classes and allows for mild derivatization of the dipoles into beta-aminoamides, beta-aminoesters, and beta-amino acids.

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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 novel flow-through column electrolytic cell was proposed as a detector to obtain current signals for supercritical fluid chromatography. The electrochemical cell consisted of two electrodes and its holder, and a working and a counter electrode were fabricated from 192 carbon strings, which were composed of 400 carbon fibers of 10 mum in diameter filled into a heat-shrinkable tube. These electrodes were placed in the center of a holder made from polyether ether ketone blocks and they were separated by polytetrafluoroethylene membrane filters. To evaluate the sensitivity of this cell, a standard solution of ferrocene was injected into the supercritical fluid chromatography system connected to the electrolytic cell. The ferrocene was eluted through a silica gel column using a mixture of a mobile phase of supercritical CO2 and a modifier of methanol containing ammonium acetate. The current peak area of ferrocene correlated to the ferrocene concentration in the range of 10?400 mumol/L (r = 0.999). Moreover, the limit of detection on the column estimated from a signal-to-noise ratio of 3 was 9.8 × 10?13 mol.

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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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In this study, new dendrimers with a ferrocene core were produced by means of a divergent method for the immobilization of the glucose oxidase enzyme (GOx). Pt(II)and Pt(IV)ions were attached to the terminal groups of dendrimers. Metal-containing dendrimers, [Fc(MGlu)2-Aph-Pt(II)]and [Fc(MGlu)2-Aph-Pt(IV)], were obtained using the ?template method? with aminophenol and Pt(II)/Pt(IV)cations. These compounds have been characterized by molar conductivity, magnetic susceptibility, FTIR, UV?Vis, 1H NMR and LC-MS methods. The GOx enzyme was immobilized on the Fc(MGlu)2, [Fc(MGlu)2-Aph-Pt(II)]and [Fc(MGlu)2-Aph-Pt(IV)]dendrimers, and the immobilized enzyme optimization parameters (substrate concentration, temperature, pH, reusability and storage capacity)were determined. Their Km (mM)and Vmax (mM.min?1)values were calculated from the Michaelis?Menten equation. The reusability of the immobilized glucose oxidase enzyme was investigated in an artificial urine medium. The research showed that [Fc(MGlu)2-Aph-Pt(II)]retains more than 61.23% of its initial activity after 10 successive cycles, which is a remarkable result.

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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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Chemical engineers ensure the efficiency and safety of chemical processes, adapt the chemical make-up of products to meet environmental or economic needs, and apply new technologies to improve existing processes. Electric Literature of 1293-65-8. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1293-65-8, Name is 1,1′-Dibromoferrocene

We report that Mn(IV)-oxo porphyrin complexes, MnIV(O)(TMP) (1) and MnIV(O)(TDCPP) (2), are capable of activating the C-H bonds of hydrocarbons, including unactivated alkanes such as cyclohexane, via an oxygen non-rebound mechanism. Interestingly, 1 with an electron-rich porphyrin is more reactive than 2 with an electron-deficient porphyrin at a high temperature (e.g., 0 C). However, at a low temperature (e.g., -40 C), the reactivity of 1 and 2 is reversed, showing that 2 is more reactive than 1. To the best of our knowledge, the present study reports the first example of highly reactive Mn(IV)-oxo porphyrins and their temperature-dependent reactivity in C-H bond activation reactions.

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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

 

Sep 2021 News You Should Know Something about 1271-48-3

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Reaction of 1,1?-ferrocenedicarbonyl chloride with 3-ethyl-2,4-dimethylpyrrole in DCM produced the half-way product, namely, the ferrocene bis(2-ketopyrrole) derivative 2 and not the expected bis(dipyrromethene) compound. The 2-ketopyrrole compound readily reacted with BF3·Et2O to produce the bis(difluoropyrrolo)-oxaborole compound, FBF, as a red/brown solid which was characterised by X-ray crystallography. 57Fe Moessbauer spectra for 2 and FBF were consistent with low-spin iron(II) (d6) ferrocene derivatives. A cyclic voltammogram for 2 in acetonitrile revealed a reversible wave at +0.31 V vs. Fc+/Fc (ferrocene-based) and an irreversible wave at -2.38 V vs. Fc+/Fc (ketopyrrole-based). The electrochemical behaviour is severely perturbed by the chelation of the BF2 groups. Alterations to the electronic properties of 2 by formation of FBF are also evident in the absorption profiles. DFT calculations [B3PW91, 6-31G(3df)] support the observed changes in the electrochemistry findings and the Moessbauer spectroscopic data. Reaction of 1,1?-ferrocenedicarbonyl chloride with 3-ethyl-2,4-dimethylpyrrole produces the bis(ketopyrrole) compound. Chelation of BF2 to the ketopyrrole units forms the difluoropyrrolo-oxaborole.

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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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Promoters are ubiquitous in industrial heterogeneous catalysts. The wider roles of promoters in accelerating catalysis and/or controlling selectivity are, however, not well understood. A model system has been developed where a heterobimetallic active site comprising an active metal (Rh) and a promoter ion (Ga) is preassembled and delivered onto a metal-organic framework (MOF) support, NU-1000. The Rh-Ga sites in NU-1000 selectively catalyze the hydrogenation of acyclic alkynes to E-alkenes. The overall stereoselectivity is complementary to the well-known Lindlar’s catalyst, which generates Z-alkenes. The role of the Ga in promoting this unusual selectivity is evidenced by the lack of semihydrogenation selectivity when Ga is absent and only Rh is present in the active site.

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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 series of aminophosphonates bearing the 1,1? -bis-substituted ferrocenyl moiety was obtained by the addition of dialkyl phosphites to an azomethine bond of Schiff bases derived from 1,1?-ferrocene-bis-carboxaldehyde. This addition led to both diastereoisomeric forms demonstrating its behaviour to be contrary to the addition to terephthalic Schiff bases, which led exclusively to a meso -form.

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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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57Fe NMR spectra of 20 ferrocene derivatives with natural abundance of 57Fe have been recorded by the conventional pulse Fourier transform technique using ferrocene as internal standard for the chemical shifts.Shift contributions of the substituents are discussed qualitatively.

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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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Chemical engineers work across a number of sectors, processes differ within each of these areas, but chemistry and chemical engineering roles are found throughout, creation and manufacturing process of chemical products and materials. Application of 1273-86-5. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1273-86-5, Name is Ferrocenemethanol

An original method combining two conductometric biosensors is proposed for the determination of total lactate, L- and D-lactate in dairy products. The biosensors were prepared through cross-linking of L-lactate oxidase from Pediococcus sp. (LODP) or a combination of LODP and horseradish peroxidase (HRP) at the surface of gold interdigitated microelectrodes using glutaraldehyde (GA) vapors. LODP is reported to catalyze specifically L-lactate oxidation into pyruvate and hydrogen peroxide in solution. In this work, we showed that LODP chiral selectivity was lost following enzyme cross-linking, rendering LODP sensor suitable for total lactate determination. Biosensor sensitivity towards both stereoisomers was 1.16 ± 0.04 muS muM-1. The addition of HRP significantly improved the linear range and stability of LODP biosensor, but also increased its sensitivity, the effect being more pronounced for D-lactate (+381%) than for L-lactate (+260%). This result was attributed to a modification in LODP chiral selectivity combined with the production of additional ions (acetate, H+ and HCO3-) via the HRP-catalyzed oxidation of pyruvate. A method, taking advantage of the difference in D- and L-lactate behaviours and combining the monoenzymatic and bienzymatic biosensors calibration data, was proposed for the calculation of their concentrations in unknown samples. Different parameters (HRP/LODP ratio, exposure time to GA vapors, pH and concentration of measurement medium) were optimized in order to achieve the best compromise between sensitivity and stability of the biosensors. The best limit of detection for L- and D-lactate, calculated as three times the signal to noise ratio was achieved with the bi-enzymatic sensor and was equal to 0.05 muM. LODP/HRP biosensor response towards L-lactate was not significantly affected by glucose, fructose and lactose. The proposed biosensors were finally applied to the determination of total lactate, D- and L-lactate concentrations in yogurt samples. Results were in good agreement with those obtained using a reference colorimetric enzymatic method.

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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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Oscillations in electrical current as a function of time have been observed in a specific temperature range in the samples of 1,1?-diacetylferrocene and 1,1?-ferrocenedicarboxylic acid with adsorbed ethanol vapor in a sandwich-type cell. The frequency of current oscillations has been found to decrease with bias voltage and sample temperature and to increase with vapor pressure. The frequency of current oscillations for the mono-group substituted derivatives is higher than the corresponding frequency for the derivatives having two substituted groups. Again, the frequency of oscillations for -COCH3 group substituted derivatives is higher than the corresponding value for -COOH group substituted derivatives. The observation of current oscillations is possibly associated with some kind of time dependent phase changes, arising from the structural nonrigidity of the molecules, in the solid-ethanol vapor system at the sample surface layer. The “ball-bearing” motion of the cyclopentadienyl rings of ferrocene unit, nature and number of substituted groups, cooperative interaction of the neighboring molecules influence the structural nonrigidity and hence the oscillatory behavior of current. Reasons are given for ruling out other models of current oscillations in semiconductors.

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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