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A copper-catalyzed, enantioselective method for the borylallylation of vinyl arenes is reported. The reaction produces enantioenriched and functionalized organoboron compounds by sequentially incorporating boryl and allyl groups onto the C – C bond of vinyl arenes. Copper-catalyzed borylative coupling of vinyl arenes with allyl phosphates successfully proceeds in a regio- and enantioselective manner in the absence of a palladium cocatalyst.

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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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Acylation of alkyl- and 1,1?-dialkylferrocene alcohols and diols as well as (3,4,4-trichlorobut-3-ene-1-ol-1-yl)-4,5-cymantrene with dichloroisothiazole- and 5-arylisoxazole-3-carbonyl chlorides has afforded esters containing 1,2-azoles fragments. Some of the obtained compounds have exhibited potentiating action in the binary mixtures with insecticides.

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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 variety of new polyaza and polyammonium ferrocene macrocyclic ligands complex and electrochemically recognise Ni2+, Cu2+ and Zn2+ transition metal cations and ATP, HPO42- phosphate anions in water.

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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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One with the surface: A method is presented for electrode modification with terminal alkynes and alkenes. Direct oxidation of these moieties leads to efficient grafting onto glassy carbon, gold, platinum, and indium tin oxide surfaces. Various ferrocenes and 5,10,15,20-(4-ethynylphenyl)porphyrin were attached in this way. 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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Using a single half-sandwich iron(II) compound, CpFe(1,2-Ph2PC6H4S)(NCMe) (Cp- = C5Me5-, 1) as a catalyst, reductive coupling of nitroarenes with olefins has been achieved by a well-defined iron(II)/(EtO)3SiH system. Through either inter- or intramolecular reductive coupling, various branched amines and indole derivatives have been directly synthesized in one-pot. Mechanistic studies showed that the catalysis is initiated by activation of nitroarenes by the iron(II) catalyst with silane, generating iron-nitrosoarene intermediate for the C-N bond coupling.

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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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Diiron nonacarbonyl oxidized a series of alpha-phenylcarbinols to their corresponding aldehydes and ketones.In addition, this resagent converted 4-methoxybenzyl alcohol to 4-methoxybenzyl ether, albeit in low yield.Under the same reaction conditions, oxidation was a minor with a group of alpha-ferrocenylcarbinols as ether synthesis was the major reaction with those substrates which could not dehydrate; however, stereoselective olefin synthesis predominated when elimination was possible.

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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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Herein, novel host-guest properties between perethylated pillar[6]arene and four kinds of ferrocene derivatives were fully investigated. NMR titrations, 2D NOESY NMR spectroscopy, and ESI-MS are used to confirm that they indeed formed stable inclusion complexes. Two precious single-crystal structures were obtained and showed that ferrocene derivatives with different chemical structures exhibit different binding modes with perethylated pillar[6]arenes.

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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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Complexation of iron(II) protoporphyrin IX (Fe2+PP) into a genetically engineered heme pocket on recombinant human serum albumin (rHSA) creates an artificial hemoprotein which can bind O2 reversibly at room temperature. Here we highlight a crucial role of a basic amino acid triad the entrance of the heme pocket in rHSA (Arg-114, His-146, Lys-190) for O 2 and CO binding to the prosthetic Fe2+PP group. Replacing His-146 and/or Lys-190 with Arg resolved the structured heterogeneity of the possible two complexing modes of the porphyrin and afforded a single O 2 and CO binding affinity. Resonance Raman spectra show only one geometry of the axial His coordination to the central ferrous ion of the Fe 2+PP.

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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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In this study, the tryptophan derivative of ferrocene-1,1?- dicarboxylic acid self-assembles in toluene to form a supramolecular nanofibrillar network structure. The ferrocene bioconjugate based nanofibers are responsive toward oxidation/reduction and show thermo and redox reversibility. Interestingly, redox-induced reversible morphological transformations between nanofiber and spheroid were observed. The self-assembly was characterized by 1H NMR spectroscopy, FT-IR spectroscopy, UV-vis spectroscopy, circular dichroism (CD), and transmission electron microscopy (TEM).

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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 family of rigid ferrocenyl-terminated redox stars has been synthesizedsby Negishi coupling, including hexa(ferrocenethynyl)benzene complexes, a dodecaferrocenyl star, and stars with extended rigid tetherssand fully characterized. Cyclic voltammetry (CV) studies of the parent complex hexa(ferrocenylethynyl) benzene, 1, show a single wave for the six-electron oxidation of 1 using Nn-Bu4PF6 as the supporting electrolyte on a Pt anode in CH2Cl2, whereas three distinct two-electron reversible CV waves are observed using Nn-Bu 4BArF4 (ArF = 3,5-C 6H3-(CF3)2,). The CV of 1,3,5-tris(ferrocenylethynyl)benzene, 11, also shows only one wave for the three-electron transfer with Nn-Bu4PF6 and three one-electron waves using Nn-Bu4BArF4. This confirms the lack of electronic communication between the ferrocenyl groups and a significant electrostatic effect among the oxidized ferrocenyl groups. This effect is not significant between paraferrocenyl groups in 1,4- bis(ferrocenylethynyl)benzene for which only a single wave is observed even with Nn-Bu4BArF4 as the supporting electrolyte. The para-ferrocenyl substituents are quite independent, which explains that two para-ferrocenyl groups are oxidized at about the same potential in a single CV wave of 1. With the additional steric bulk introduced with a methyl substituent on the ferrocenyl group, however, even the para-methylferrocenyl groups are submitted to a small electrostatic effect splitting the six-electron transfer into six single-electron waves, probably because of the overall steroelectronic constraints. Contrary to 11, 1,3-bis(ferrocenylethynyl)benzene and related complexes with a third, different substituent in the remaining meta position different from a ferrocenylethynyl only show a single two-electron wave using Nn-Bu4BArF4, which is attributed to the transoid conformation of the ferricinium groups minimizing the electrostatic effect. This shows that, in 11, it is the steric frustration that is responsible for the electrostatic effect, and the same occurs in 1. In several cases, DeltaEp is much larger than the expected 60 mV value, characterizing a quasi-reversible (i.e., relatively slow) redox process. It is suggested that this slower electron transfer be attributed to conformational rearrangement of the ferrocenyl groups toward the transoid position in the course of electron transfer. Thus both the thermodynamic and kinetic aspects of the electrostatic factor (isolated from the electronic factor), including the frustration effect, are characterized. The distinction between the electronic communication and through-space electrostatic effect was made possible in all of these complexes in which the absence of wave splitting using a strongly ion-pairing electrolyte shows the absence of significant electronic communication, and was confirmed by the new frustration phenomenon.

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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