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An efficient and flexible asymmetric synthesis of planar chiral 2-mono- and 2,2?-disubstituted 1,1?-bisbenzoylferrocenes 4 and 6 is reported. Key step is a highly diastereoselective ortho-metalation of 1,1?-bisbenzoylferrocene 1 via the corresponding bis-SAMP-hydrazone 2 (de?96%), followed by trapping with various carbon, silicon, phosphorus and sulfur electrophiles. Cleavage of the monosubstituted hydrazones 3 led to monosubstituted ketones 4 (ee?98%). Further ortho-substitution of the hydrazones 3 afforded 2,2?-disubstituted hydrazones 5, which could be cleaved to disubstituted ferrocenyl diketones 6 (ee?99%). The new methodology allows a broad and flexible fine-tuning of ferrocenyl ligands desired in asymmetric catalysis. Ozonolysis or reductive hydrazone cleavage using TiCl3 or SnCl2 were the methods of choice to remove the auxiliary.

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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 new potentially C3-symmetric phosphine ligand ‘manphos’ has been obtained and fully characterized. The ligand which is a tri-ferrocenyl-tetra-phosphine is obtained in a simple and effective two step synthesis starting from 1,1?-dibromoferrocene via the intermediate compound tris-(1?-bromoferrocenyl)phosphine or alternatively via 1′-bromo-1-diphenylphosphinoferrocene. The iso -propylphosphino-analogue of manphos, tris-(1′-diisopropylphosphinoferrocenenyl)phosphine, has also been obtained, in addition to several functionalised derivatives of triferrocenylphosphine where the ferrocene rings have been substituted in the 1?-position.

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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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Enzymes are biological catalysts with many industrial applications, but natural enzymes are usually unsuitable for industrial processes because they are not optimized for the process conditions. The properties of enzymes can be improved by directed evolution, which involves multiple rounds of mutagenesis and screening. By using mathematical models to predict the structure?activity relationship of an enzyme, and by defining the optimal combination of mutations in silico, we can significantly reduce the number of bench experiments needed, and hence the time and investment required to develop an optimized product. Here, we applied our innovative sequence?activity relationship methodology (innov’SAR) to improve glucose oxidase activity in the presence of different mediators across a range of pH values. Using this machine learning approach, a predictive model was developed and the optimal combination of mutations was determined, leading to a glucose oxidase mutant (P1) with greater specificity for the mediators ferrocene?methanol (12-fold) and nitrosoaniline (8-fold), compared to the wild-type enzyme, and better performance in three pH-adjusted buffers. The kcat/KM ratio of P1 increased by up to 121 folds compared to the wild type enzyme at pH 5.5 in the presence of ferrocene methanol.

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Ferrocenylmethy 1,2-dithiolane-3-pentanoate, which can be used to modify a gold electrode surface, was prepared by a condensation reaction with hydroxymethylferrocene and 1,2-dithiolane-3-pentanoic acid (D, L-alpha-lipoic acid). The condensation product has an 1,2-dithiolane ring which adheres to gold surfaces and a ferrocenyl group which is a redox site. The ferrocene rings on the modified electrode were electroactive in both acetonitrile and aqueous media.

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The complexation of trimethyl(ferrocenylmethyl)ammonium hexafluorophosphate 1*(BF6), heptyldimethyl(ferrocenylmethyl)ammonium bromide 2*(Br) and ferrocenylmethanol 3 by sulfonated calix<6>arene host was investigated in aqueous media using electrochemical and 1H NMR spectroscopic techniques; the binding interactions between the calixarene host and the surveyed guests are similar to those operating in the complexation of organic compounds by cyclodextrin or cyclophane in aqueous media.

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Layered transition metal dichalcogenides (TMDs) have received a great deal of attention due to fact that they have varied band gap, depending on their metal/chalcogen composition and on the crystal structure. Furthermore, these materials demonstrate great potential application in a myriad of electrochemical technologies. Heterogeneous electron transfer (HET) abilities of TMD materials toward redox-active molecules occupy a key role in their suitability for electrochemical devices. Herein, we introduce a promising biosensing strategy based on improved heterogeneous electron transfer rate of WS2, WSe2, and WTe2 nanosheets exfoliated using tert-butyllithium (t-BuLi) and n-butyllithium (n-BuLi) intercalators decorated with vertically aligned TiO2 nanoplatelets. By comparison of all the nanohybrids, decoration of TiO2 on t-BuLi WS2 (TiO2@t-BuLi WS2) results in the fastest HET rate of 5.39 × 10-3 cm s-1 toward ferri/ferrocyanide redox couple. In addition, the implications of decorating tungsten dichalcogenides (WX2) with TiO2 nanoplatelets in enzymatic biosensor applications for H2O2 detection are explored. TiO2@t-BuLi WS2 outperforms all other nanohybrid counterparts and is demonstrated to be an outstanding sensing platform in enzyme-based biosensor with wide linear range, low detection limit, and high selectivity. Such conceptually new electrocatalytic detection systems shall find the way to the next generation biosensors.

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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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Cocrystals derived from 1,1?-bis(ethenyl-4-pyridyl)ferrocene (1) and resorcinol/phloroglucinol and a crystal of 1,1?-bis-(ethenyl-4-quinolinyl)ferrocene (5) have been studied with the aim of engineering crystalline NLO materials. X-ray structure analyses revealed a NLO active syn-type molecular conformation of 1 and 5 via hydrogen bonding with resorcinol/phloroglucinol and pi-pi interaction between quinoline rings, respectively. For 5, all molecular dipoles are aligned in the same direction and the SHG efficiency is about 4 times that of urea. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

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To immobilize enzymes at the surface of a nanoparticle-based electrochemical sensor is a common method to construct biosensors for non-electroactive analytes. Studying the interactions between the enzymes and nanoparticle support is of great importance in optimizing the conditions for biosensor design. This can be achieved by using a combination of analytical methods to carefully characterize the enzyme nanoparticle coating at the sensor surface while studying the optimal conditions for enzyme immobilization. From this analytical approach, it was found that controlling the enzyme coverage to a monolayer was a key factor to significantly improve the temporal resolution of biosensors. However, these characterization methods involve both tedious methodologies and working with toxic cyanide solutions. Here we introduce a new analytical method that allows direct quantification of the number of immobilized enzymes (glucose oxidase) at the surface of a gold nanoparticle coated glassy carbon electrode. This was achieved by exploiting an electrochemical stripping method for the direct quantification of the density and size of gold nanoparticles coating the electrode surface and combining this information with quantification of fluorophore-labeled enzymes bound to the sensor surface after stripping off their nanoparticle support. This method is both significantly much faster compared to previously reported methods and with the advantage that this method presented is non-toxic. [Figure not available: see fulltext.].

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The preparation of 1,1?-bis(beta-hydroxyethyl)ferrocene (1) by oxidation of 1,1?-divinylferrocene is described. Compound 1 has been characterized by 1H and 13C{1H} NMR, and cyclic voltammetry. The electrochemical data are compared to ferrocene and the closely related 2-ferrocenylethanol, 2.

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Reaction of ferrocene-1,1?-dicarbaldehy de and propylenediamine yields the Schiff-base derivative 1,1?-(2,6-diazahepta-1,6-diene)-ferrocene (1). The molecular structure of 1 has been determined by single crystal X-ray analysis. It crystallises in the monoclinic system, space group P21/c, a=13.507(3), b=9.800(2), c=10.086(2) A, beta=110.81(3), Z=4 and V=1248.0(5) A3. Refinement of the atomic parameters by least-squares techniques gave a final R factor of 0.074 for 1588 observed reflections having 1>2sigma(1), Hydrogenation of 1 with LiA1H4 results in the parent amine 1,1?-(2,6-diazaheptane)ferrocene (2). The protonation of 2 has been investigated by potentiometry in water in the pH range 11-6. At pH lower than 6, 2 is unstable in solution. The E1/2 potential for 2 is pH-dependent (E1/2(pH 11) = 255, E1/2(pH 6) =435 mV). A similar behaviour was also observed in THF:water (60:40 vol./vol.). The electrochemical behaviour for 1 and 2 has also been studied in CH2Cl2.

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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