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A series of ferrocene-containing mono- and bis-dihydropyrimidines (DHP’s) were prepared by boric acid mediated three-component Biginelli reactions of formyl- and 1,1?-diformylferrocene, 1,3-dioxo-components and urea. A few further transformations including hydrogenolysis of a benzyl 4-ferrocenyl-DHP-5-carboxylate were also performed. Novel cis-fused saturated pyrimido[4,5-d]pyrimidine-2,7(1H,3H)-diones incorporating [3]-ferrocenophane moiety were constructed by means of iron(III)-catalyzed Biginelli-like condensations of 1,1?-diformylferrocene with urea and in situ generated methyl ketone-derived silyl enol ethers. The structures of the new compounds were established by IR and NMR spectroscopy, including HMQC, HMBC and DEPT measurements.

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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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The invention concerns a process for the manufacture of substituted propionic acids comprising providing a substrate of formula (I): And subjecting the substrate to enantioselective hydrogenation under enantioselective hydrogenation conditions in the presence of an enantioselective hydrogenation catalyst comprising a catalyst ligand having a metallocene group with a chiral phosphorus or arsenic substituent to provide in enantiomeric excess a product of formula (II): or its enantiomer or if applicable its diastereomer.

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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 an improved synthesis of 1,1?-diaminoferrocene, employing the reduction of 1,1?-diazidoferrocene with H2-Pd/C, along with extensive characterization data for both compounds. Diaminoferrocene undergoes a reversible 1e- oxidation in CH3CN at a potential of -602 mV vs Fc0/+, one of the most negative redox potentials for a ferrocene derivative. The chemical reversibility of this process was confirmed by isolation of the stable, 17-electron [Fc(NH2)2]+ cation as PF6-, OTf-, and TCNE- salts. In the solid state, diaminoferrocene exists in two conformations: one with the NH2 groups eclipsed, and the other with the NH2 groups offset by one-fifth turn around the Cp-Fe-Cp axis. Diazidoferrocene, on the other hand, exhibits only the fully eclipsed conformation in the solid state. The Fe-Cp(centroid) vectors in the diazidoferrocene molecules are roughly aligned with the crystallographic c-axis, and the molecules form layers perpendicular to this axis. The compound is thermally unstable at elevated temperatures, and rapid heating above its melting point results in explosion.

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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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Point-of-care testing (POCT) of neurotransmitters, such as dopamine (DA) and 5-hydroxytryptamine (5-HT), can be used for early diagnosis of neurological diseases. Among various POCT platforms, electrochemical method-based platforms have attracted increasing interest owning to their high detection sensitivity and specificity as well as fast response time. In this work, we developed a portable electrochemical POCT platform for detection of neurotransmitters, which is based on integration of a three-dimensional (3D) gold nanoparticles/carbon nanotubes (AuNPs/CNTs) sponge synthesized by a simple in-situ growth and eco-friendly ice-templating method modified screen-printed electrode with a miniaturized USB electrochemical analyzer. We demonstrated the good performance of the portable electrochemical platform for detection of two typical neurotransmitters, i.e., DA and 5-HT, with detection sensitivities of 1.02 muA muM?1 cm?2 and 0.55 muA muM?1 cm?2, and detection limits of 0.06 muM and 0.30 muM for DA and 5-HT, respectively. We further verified the feasibility and practicability of the platform by simultaneous detection of DA and 5-HT in spiked saliva. The developed portable electrochemical platform provides a simple and user-friendly way for early diagnosis of neurological diseases in the future, especially at point of care.

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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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Gold(i) phosphine complexes are often used in catalysis, but the role of their auxiliary ligands still remains poorly understood. Thus, building on our previous research, we prepared a series of Au(i) complexes [Au2(mu-R2PfcCN)2][SbF6]2 (fc = ferrocene-1,1?-diyl) to assess the effect of phosphine groups PR2 on the catalytic properties of these highly catalytically active, dimeric compounds. Catalytic testing in Au-mediated cyclisation of N-propargyl amides to 2-substituted 5-methyleneoxazolines showed that weaker donating phosphines gave rise to more active, albeit partly destabilised, catalysts. Nevertheless, thanks to their self-stabilisation by reversible nitrile coordination, [Au2(mu-R2PfcCN)2]+ cations readily converted into catalytically active species (by dissociation) and, in addition, remained catalytically active even at very low metal loadings. The experimental results were supported by the trends in 1JPSe coupling constants for R2P(Se)fcCN as a measure of ligand basicity, and by DFT calculations.

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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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1,1?-Diacetylferrocene bis(p-toluenesulfonylhydrazone) and its complex with divalent palladium of composition Pd2LCl2 were synthesized. Infrared, electronic, and 1 H NMR spectroscopy indicate that the semichelate has a cyclopaladinized structure. It is suggested that several forms of the complex exist in solution. Copyright

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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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The solubilities of ferrocene, ferrocenylcarbinol, methylferrocenylcarbinol, and dimethylferrocenylcarbinol in water at 10-60C are determined. The thermodynamic parameters of the dissolution process are calculated.

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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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The enantiomerically pure dibromoferrocene 3 [(Sp,S p)-1,1?-dibromo-2,2?-di(isopropyl)ferrocene], equipped with two iPr groups in alpha positions, was prepared using known “Ugi amine” chemistry. Species 3 was targeted in order to gain access to new [1]ferrocenophanes ([1]FCPs) to be used as monomers for ring-opening polymerization. The iPr groups on the sandwich unit were introduced to stabilize bridging moieties, as well as to increase solubilities of targeted metallopolymers. The planar chiral dibromide 3 can quantitatively be lithiated at 0 C [2 equiv nBuLi, hexanes/thf (9:1), 30 min]. Salt-metathesis reactions with respective element dichloride species gave chiral [1]FCPs with a variety of bridging moieties [ERx=Ga[2-(Me2NCH 2)C6H4] (4 a), SiMe2 (4 b), SntBu2 (4 c), BNiPr2 (4 d)]. The new [1]FCPs were fully characterized including single-crystal X-ray analysis. The stabilizing iPr groups on the Cp rings increase the thermal stabilities of 4 b-d compared to known [1]FCPs, equipped with the same bridging moieties. All three compounds 4 b-d are volatile and could be isolated by vacuum sublimation. Our new approach to [1]FCPs has the potential to overcome many of the existing difficulties in ferrocenophane chemistry, such as limited stability of starting monomers and low solubilities of resulting polyferrocenes. Closing the gap: The preparation of [1]ferrocenophanes with a variety of bridging elements was accomplished by using chiral ferrocene derivatives (see scheme). The isopropyl groups on the sandwich unit serve as protective and solubilizing moieties. The new synthetic approach is superior to the common synthesis of [1]ferrocenophanes, when dilithioferrocene-tmeda is used as the starting material. Copyright

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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 synthetic procedure based on the aza-Wittig reaction of alpha-azidoacetyl ferrocene or 1,1?-bis(alpha-azidoacetyl)ferrocene with mono-, di-, and triacyl chlorides and triphenylphosphine has been developed to prepare the new homotrimetallic ferrocene complexes 6, 9, and 10 containing at least two oxazole rings in the conjugation chain. Complexes 9 and 10 exhibited three and two reversible redox processes, respectively, indicating significant electrostatic interaction between the iron centers in these complexes. Protonation properties of complexes 9-13 have been assessed by use of 1H NMR and cyclic voltammetry measurements.

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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 hemin/graphene composite, prepared by mixing an aqueous solution of graphene oxide (GO) with hemin and sonicating the suspension for 5 h at room temperature, was investigated for olefination of aldehydes using ethyl diazoacetate in the presence of triphenylphosphine. Efficient olefination of aromatic aldehydes with high (E)-selectivity was obtained, revealing that rGO/hemin is a promising heterogeneous catalyst for the olefination reaction. The as-synthesized catalyst could easily be recovered from the reaction mixture and was subsequently used for several runs without any significantly loss in activity and selectivity.

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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