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Herein is described the synthesis of (+)-camphor derivatives containing sulfonamide groups, ferrocenylmethylidene or arylidene moieties. The obtained derivatives were tested against seven human cancer cells lines, namely BV-173, K-256a, NB-4, A549, H1299, MCF-7, and MDA-MB231, and two normal human cell lines, HEK293 and HUVEC, in order to determine their activity against malignant cells. Some of them exhibit IC50 values below 10 muM in at least one of the cancer cell lines. Ferrocenylmethylidene ketone 16 can be outlined as the most potent and selective in the current study (IC50 for cancer cells-up to 4.0 muM; IC50 for HEK293 and HUVEC-68 and 69 muM, respectively). There is a clear trend showing that the presence of a conjugated ferrocenylmethylidene group is essential for the cytotoxicity, however different sulfonamide substituents and derivatization of the carbonyl group can modify the activity. Thus, this class of compounds could have good prospects for further structural optimisation.

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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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Drug resistance in bacteria is becoming a significant threat to global public health, and the development of novel and efficient antibacterial compounds is urgently needed. Recently, rhodium complexes have attracted attention as antimicrobial agents, yet their antibacterial mechanism remains unknown. In this study, we observed that the dirhodium (II) complex Rh2Ac4 inhibited Streptococcus. pneumoniae growth without significant cytotoxic side-effects on host cells in vitro. We subsequently investigated the antibacterial mechanism of Rh2Ac4 using iTRAQ-based proteomics combined with cellular and biochemical assays. Bioinformatics analysis on the proteomic alterations demonstrated that six molecular functional groups, including metal ion binding and twelve metabolic pathways, were significantly affected after treatment with Rh2Ac4. The interaction network analysis of metal ion binding proteins suggested that Rh2Ac4 decreased the protein expression levels of SPD_1652, SPD_1590 and Gap, which are associated with haem uptake/metabolism. Cellular and biochemical assays further confirmed that Rh2Ac4 could be taken up by bacteria via the PiuABCD haem-uptake system. The structurally similar Rh complex may compete with Fe-haem to decrease Fe-uptake via the PiuABCD system, disrupting iron metabolism to exert its antibacterial activity against S. pneumoniae. These data indicate that Rh2Ac4 is a promising new drug for the treatment of S. pneumoniae infections.

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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 synthesis and characterization of a series of carbosilane-supported ferrocenyl phosphine ruthenium complexes of type SiMe4-n(Fe(eta5-C5H4SiMe2(CH2)3)((eta5-C5H4PR2)RuCl2(eta6-p-cymene)))n (p-cymene = 1-i-Pr-4-Me-C6H4; n = 2: 10a, R = Ph; 10b, R = cC6H11; 10c, R = 2-(5-Me)C4H2O); n = 4: 11a, R = Ph; 11b, R = cC6H11; 11c, R = 2-(5-Me)C4H2O)) is described. For comparative reasons, the non-immobilized ferrocenyl phosphine ruthenium complexes [FcPR2(RuCl2(eta6-p-cymene))] (Fc = Fe(eta5-C5H4)(eta5-C5H5); 9a, R = Ph; 9b, R = cC6H11; 9c, R = 2-(5-Me)C4H2O) were prepared. The molecular structure of 9c in the solid state is reported confirming the expected tetrahedral coordination sphere about the phosphorus atom and the “piano-stool” geometry about ruthenium. The ruthenium complexes 9-11 are catalytically active in the addition of benzoic acid to propargyl alcohol to form beta-oxopropyl benzoate. The obtained activities and productivities show that a good solubility of the catalyst is necessary for a successful catalytic reaction. Furthermore, the rate of the reaction can be influenced by using less basic and electron-withdrawing phosphine ligands.

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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 stereoelectronic influence of phosphine substituents on the coordination and catalytic properties of phosphinoferrocene carboxamides was studied for the model compounds R2PfcCONHMe (1a-d), where fc = ferrocene-1,1?-diyl and R = i-Pr (a), t-Bu (b), cyclohexyl (Cy; c), Ph (d), using experimental and DFT-computed parameters. The electronic parameters were examined via 1JSeP coupling constants determined for R2P(Se)fcCONHMe (6a-d) and C?O stretching frequencies of the Rh(I) complexes trans-[RhCl(CO)(1-kappaP)2] (7a-d); the steric properties of 1a-d were assessed through Tolman?s ligand cone angles (theta) and solid angles (Omega). Generally, a very good agreement between the calculated and experimental values was observed. Whereas the donor ability of the amidophosphines was found to increase from 1d through 1a,c to 1b, the trends in steric demand suggested by the two parameters differed, reflecting the different spatial properties of the phosphine substituents. In situ NMR studies and catalytic tests on the Suzuki-Miyaura cross-coupling of 4-bromoanisole with a bicyclic 4-tolylborate to give 4-methyl-4?-methoxybiphenyl using [Pd(eta2:eta2-cod)(eta2-ma)] (cod = cycloocta-1,5-diene, ma = maleic anhydride) as a Pd(0) precursor revealed that different Pd-1 species (precatalysts) were formed from different ligands and participated in the reaction. Specifically, the bulky and electron-rich donor 1b favored the formation of [Pd(1b)(ma)], while the remaining ligands provided the corresponding bis-phosphine complexes [Pd(1)2(ma)]. The best results in terms of catalyst longevity and efficacy were observed for ligands 1a,c.

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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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Electrochemical studies of the free ferrocenylphosphine ligands FcCH2PR2 (Fc=(eta5-C5 H5)Fe(eta5-C5H4); R=Ph, CH2OH and CH2CH2CN) and some phosphine oxide, phosphine sulfide, phosphonium and metal derivatives are described. The free ligands exhibit complex voltammetric responses due to participation of the phosphorus lone pair in the redox reactions. Uncomplicated ferrocene-based redox chemistry is observed for PV derivatives and when the ligands are coordinated in complexes cis-PtCl2[FcCH2P(CH2OH) 2], PdCl2[FcCH2P(CH2OH) 2], [Au{FcCH2P(CH2OH)2} 2]Cl, RuCl2(eta6-C10 H14)[FcCH2P(CH2OH)2] and RuCl2(eta6-C10H14) (FcCH2PPh2). The reaction pathways of the free ligands after one-electron oxidation have been examined in detail using voltammetry, NMR spectroscopy and electrospray mass spectrometry. Direct evidence for formation of a P-P bonded product is presented.

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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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Ferrocenylalkyl nitro-imidazoles (4a-h, 5a-h) were prepared via the regiospecific reaction of the alpha-(hydroxy)alkyl ferrocenes, FcCHR (OH) (1a?h; Fc = ferrocenyl; R = H, Me, Et, Pr, i-Pr, Ph, ortho-Cl-Ph, ortho-I-Ph), with nitro-imidazoles in aqueous organic medium (H2O-CH2Cl2) at room temperature in the presence of HBF4, within several minutes in good yields. X-ray structural data for racemic (R,S)-1-N-(benzyl ferrocenyl)-2-methyl-4-nitroimidazole (5f) were determined. The resulting enantiomers were resolved into enantiomers by analytical HPLC on modified amylose or cellulose chiral stationary phases. The viabilities of 4b, 4d, 5b, 5c in vitro, and in experiments in vivo antitumor effects of 1-N-ferrocenylethyl-4-nitroimidazole (4b) against murine solid tumor system Ca755 carcinoma were evaluated.

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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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You could be based in a university, combining chemical research with teaching; in a pharmaceutical company, working on developing and trialing new drugs; Application of 1271-48-3, or in a public-sector research center, helping to ensure national healthcare provision keeps pace with new discoveries.In a article, mentioned the application of 1271-48-3, Name is 1,1′-Ferrocenedicarboxaldehyde, molecular formula is C12H10FeO2

Meso-substituted corroles bearing directly linked ferrocene unit have been synthesized for the first time. Among various methods studied, only the condensation of pentafluorophenyldipyrromethane with a formylferrocene led to this type of product. A triad containing corrole and porphyrin bridged with ferrocene has been obtained by a convergent approach. Bilanes were used as crucial substrates in the porphyrin-forming step. For the first time it was shown that H2O-MeOH-HCl conditions are suitable for preparation of various 10-(formylaryl)corroles via the direct condensation of aromatic dialdehydes with dipyrromethanes. Electrochemical studies of 10-ferrocenyl-5,15-bis(pentafluorophenyl)corrole support the possibility of intramolecular electron transfer from the corrole to the ferrocene system after the electrode oxidation of the ferrocene to a ferrocenium cation. We have studied the structure of 1-(corrolyl)-1?-(porphyrinyl)ferrocene by 1H NMR and UV-Vis. NMR spectra show that this compound has more conformational freedom than analogous, previously studied bis- porphyrinylferrocenes. Absorption spectra suggest the lack of strong electronic interaction between ferrocene and porphyrinoids for dyads and significant conjugation for the triad. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

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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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You could be based in a university, combining chemical research with teaching; in a pharmaceutical company, working on developing and trialing new drugs; Application of 1273-86-5, or in a public-sector research center, helping to ensure national healthcare provision keeps pace with new discoveries.In a article, mentioned the application of 1273-86-5, Name is Ferrocenemethanol, molecular formula is C11H3FeO

A new form of high surface bioelectrode based on electrospun gold microfiber with -immobilized glucose oxidase was developed. The gold fibers were prepared by electroless deposition of gold nanoparticles on a poly(acrylonitrile)-HAuCl4 electrospun fiber. The material was characterized using electron microscopy, XRD and BET, as well as cyclic voltammetry and biochemical assay of the immobilized enzyme. The surface area of the gold microfibers was 2.5 m2/g. Glucose oxidase was covalently crosslinked to the gold surface using cystamine monolayer and glutardialdehyde, and portrayed characteristic catalytic currents for oxidizing glucose using a ferrocene methanol mediator. Limit of detection of glucose is 0.1 mM. The K m of the immobilized enzyme is 10 mM, in accordance with other reports of immobilized glucose oxidase. The microfiber electrode was reproducible and showed correlation between fiber weight, cathodic current and enzymatic loading.

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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 reductive deoxygenation of alpha-ferrocenyl aldehydes, ketones, alcohols, and carboxylic acid into the corresponding alkylferrocenes is accomplished solely by borane-dimethyl sulfide (BMS) in the absence of any Lewis acid catalyst. This is the first example of such reactivity of BMS. The present method allows the synthesis of alkylferrocenes including those bearing terminally functionalized pendant chains.

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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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Resonance Raman spectra of beta-hematin and hemin are reported for a range of excitation wavelengths including 406, 488, 514, 568, 633, 780, 830, and 1064 nm. Dramatic enhancement of A1g modes (1570, 1371, 795, 677, and 344 cm-1), ring breathing modes (850-650 cm-1), and out-of-plane modes including iron-ligand modes (400-200 cm-1) were observed when irradiating with 780- and 830-nm laser excitation wavelengths for beta-hematin and to a lesser extent hemin. Absorbance spectra recorded during the transformation of hemin to beta-hematin showed a red-shift of the Soret and Q (0-1) bands, which has been interpreted as excitonic coupling resulting from porphyrin aggregation. A small broad electronic transition observed at 867 nm was assigned to a z-polarized charge-transfer transition dxy ? eg(pi*). The extraordinary band enhancement observed when exciting with near-infrared excitation wavelengths in beta-hematin when compared to hemin is explained in terms of an aggregated enhanced Raman scattering hypothesis based on the intermolecular excitonic interactions between porphyrinic units. This study provides new insight into the electronic structure of beta-hematin and therefore hemozoin (malaria pigment). The results have important implications in the design and testing of new anti-malaria drugs that specifically interfere with hemozoin formation.

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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