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An organocatalyzed metal-free, direct olefination of aldehydes with vinyliodonium salts has been achieved by an N-heterocyclic carbene-promoted C-H bond activation. The reaction proceeds under very mild conditions, delivering a range of (hetero)aryl-vinyl ketones in good yields. The retention of the double bond configuration is uniformly observed, and the application of 2-methoxyphenyl auxiliary group in iodonium salts secures a complete selectivity of the vinyl transfer.

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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 diffusion rates of seven ferrocene derivatives have been estimated in polyelectrolyte PEG · LiClO4 by using non-steady-state chronoamperometry. The Dapp of ferrocene derivatives increases with temperature, and the dependency of Dapp on temperature obeys the Arrhenius equation. The Dapp of ferrocene derivatives decreases with increasing size of electroactive species. The DeltaDapp values of DT>Tm and DT Tm in the polyelectrolyte. On the other hand, the diffusion behaviour of ferrocene derivatives is qualitatively analyzed by using cyclic voltammetry. Copyright

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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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Kinetics of photoinduced electron transfer from a series of electron donors to the triplet excited states of a series of nonplanar porphyrins, hydrochloride salts of saddle-distorted dodecaphenylporphyrin ([H 4 DPP]Cl 2 ), tetrakis(2,4,6-trimethylphyenyl)porphyrin ([H 4 TMP]Cl 2 ), tetraphenylporphyrin ([H 4 TPP]Cl 2 ), and octaphenylporphyrin ([H 4 OPP]Cl 2), were investigated in comparison with those of a planar porphyrin, zinc [tetrakis(pentafluorophenyl)]porphyrin [Zn(F 20 TPP)(CH 3 CN)], in deaerated acetonitrile by laser flash photolysis. Theresulting data were evaluated in light of the Marcus theory of electron transfer, allowing us to determine reorganization energies of electron transfer to be 1.21 eV for [H 4 TMP]Cl 2 ,1.29 eV for [H 4 TPP]Cl 2 , 1.45 eV for [H 4 OPP]Cl 2 , 1.69 eV for [H 4 DPP]Cl 2 , and 0.84 eV for [Zn(F 20 TPP)(CH 3 CN)]. The reorganization energies exhibited a linear correlation relative to the out-of-plane displacements, which represent the degree of nonplanarity. The rate of electron-transfer reduction of diprotonated porphyrins is significantly slowed down byconformational distortions of the porphyrin ring. This indicates that t he reorganization energy of electron transfer is governed by structural change, giving a larger contribution of inner-sphere bond reorganizationenergy rather than outer-sphere solvent reorganization energy.

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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 description of the preparation and characterization of 25 mum diameter modified carbon paste-based Cu2+ ion-selective electrodes are reported. The electrodes have a linear potential response within the 10-3 to 10-6 M range and a 16 s response time. A substantial benefit of this new type of ion-selective microelectrode (ISME) is the capability to use them as a dual function tip, in either the amperometric or the potentiometric mode of scanning electrochemical microscopy (SECM). The applications reported also support the usefulness of copper ion-selective carbon paste microelectrodes in SECM potentiometric imaging.

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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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Fc (ferrocene)-functionalized citric acid dendrimers were successfully synthesized via the reaction of citric acid dendrimers with ferrocene methanol using dicyclohexylcarbodiimide. ClOC?PEG?COCl was used as the core, and the related dendrimers were synthesized divergently. Subsequently, each generation was functionalized with ferrocene methanol. The obtained Fc-dendrimers were characterized by 1H NMR and FTIR spectroscopy. We have studied the relocation of electrons around the peripheries of dendrimers and between their redox terminals and electrodes by studies of the electrochemistry of dendrimers awarding metallocenes as functional?s groups, because these compounds can be stabilized together their oxidized and their reduced states. In addition, the voltammograms of each Fc-functionalized generation were studied and the influence of scan rate, solvent, and [Fe] unit and the concentration of the Fc-dendrimers were investigated.

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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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Presented herein is a simple, robust, and label-free homogeneous electrochemical sensing platform constructed for the detection of protein kinase activity and inhibition by integration of carboxypeptidase Y (CPY)-assisted peptide cleavage reaction and vertically ordered mesoporous silica films (MSFs). In this sensing platform, the substrate peptide composed of kinase-specific recognized sequence and multiple positively charged arginine (R) residues was ingeniously designed. In the presence of protein kinase, the substrate peptide was phosphorylated and then immediately resisted CPY cleavage. The phosphorylated peptide could be effectively adsorbed on the negatively charged surface of MSFs modified indium-tin oxide (ITO) electrode (MSFs/ITO) by noncovalent electrostatic attraction. The adsorbed peptide was subsequently used as a hamper to prevent the diffusion of electroactive probe (FcMeOH) to the electrode surface through the vertically aligned nanopores, resulting in a detectable reduction of electrochemical signal. As demonstrated for the feasibility and universality of the sensing platform, both protein kinase A (PKA) and casein kinase II (CK2) were selected as the models, and the detection limits were determined to be 0.083 and 0.095 UmL-1, respectively. This sensing platform had the merits of simplicity, easy manipulation, and improved phosphorylation and cleavage efficiency, which benefited from homogeneous solution reactions without sophisticated modification or immobilization procedures. In addition, given the key role of inhibition and protein kinase activity detection in cell lysates, this proposed sensing platform showed great potential in kinase-related bioanalysis and clinical biomedicine.

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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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Catalytic enantioselective conjunctive cross-coupling between 9-BBN borate complexes and aryl electrophiles can be accomplished with Ni salts in the presence of a chiral diamine ligand. The reactions furnish chiral 9-BBN derivatives in an enantioselective fashion and these are converted to chiral alcohols and amines, or engaged in other stereospecific C?C bond forming 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

 

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Condensation of 1,1?-diacetyl ferrocene with 2-amino-5-methylthiazole in 1: 2 molar ratio yields a ferrocenyl Schiff base ligand 1,1?-bis(Z)-N-ethyldiene-5-methylthiazol-2-amine ferrocene (L). This ligand forms 1:1 complexes with La(III), Ce(III), Pr(III) and Gd(III) nitrate in a good yield. Characterization of the ligand and complexes were carried out using infrared, nuclear magnetic resonance, mass spectra, electronic absorption, magnetic susceptibility, molar conductivity and elemental analysis. The cytotoxicity and in vitro anticancer evaluation of the ligand and its complexes have been assessed against four different human tumor cell lines (MCF-7, HepG2, A549 and HCT116). The results revealed that the prepared compounds exert their actions in HepG2 and MCF-7 through inhibition of the activity of both urokinase and histone deacetylase (HDAC). Pr-complex revealed promising anticancer activity compared to the activity of the commonly used anticancer drug, doxorubicin.

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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 heat capacities of acetylferrocene, 1,1?-diacetylferrocene, and 1,1?-diethylferrocene were investigated by low-temperature adiabatic calorimetry in the temperature range from 5 to 300 K and their thermodynamic functions were calculated. The enthalpies of combustion of the substances were determined by calorimetry of combustion, and the thermodynamic functions of their formation were calculated by quantum chemistry methods. Inter- and intramolecular interactions of the ferrocene derivatives were also studied by the methods of molecular mechanics and molecular dynamics.

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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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Mesobiliverdin IXalpha dimethyl ester (7) was obtained by hydrogenation of protobiliverdin IXalpha dimethyl ester (8).Zinc 5-oxamesoporphyrin IX dimethyl ester tetrafluoroborate (6) was prepared by the cyclization of 7 with zinc acetate in acetic anhydride followed by a treatment with aqueous sodium tetrafluoroborate.Bis(pyridine) mesoverdohemochrome IXalpha dimethyl ester (4) was obtained by the cyclization of 7 with both iron(II) sulfate and iron(III) chloride in acetic anhydride containing a small amount of pyridine.Bis(tosylmethyl isocyanide)mesoverdohemochrome IXalpha dimethyl ester (5) was prepared by the addition of excess tosylmethyl isocyanide (TsCH2NC) to 4.Both 4 and 5 reacted with ammonia to give iron(III) 5-azamesoporphyrin IX dimethyl ester (10).The Moessbauer spectra of bis(pyridine) verdohemochromes (4, 13, and 14) showed doublet peaks having parameters of delta=0.41-0.43 mm s-1 and DeltaEQ=1.24-1.26 mm s-1, indicating that the oxidation states of the central irons of these complexes are iron(II).Bis(TsCH2NC) verdohemochromes (5,15, and 17) showed single peaks having parameters of delta=0.21-0.28 mm s-1.Unstable intermediate and stable final bis(TsCH2NC) octaethyl verdohemochromes, obtained by the addition of TsCH2NC to 4, were compared with the 1H NMR and Moessbauer spectra.

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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