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A photoinduced copper-catalyzed three-component reaction involving carbohalide, alkene and amine has been developed, leading to valuable fluoroalkyl-containing amines. A sole inexpensive CuCl is used as the photo- and coupling catalyst. A broad array of substrates are capable coupling partners. The diverse method is compatible with a broad range of functional groups and can be further applied to the late-stage functionalization of bioactive pharmaceuticals.

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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 describe the synthesis, binding, and electrochemical properties of ferrocene-conjugated oligonucleotides (Fc-oligos). The key step for the preparation of Fc-oligos contains the coupling of vinylferrocene to 5-iododeoxyuridine via Heck reaction. The Fc-conjugated deoxyuridine phosphoramidite was used in the Fc-oligonucleotide synthesis. We show that thiol-modified Fc-oligos deposited onto gold electrodes possess potential ability in electrochemical detection of DNA base mismatch.

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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 facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt3)4 (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt 3)4, but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Bronsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.

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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 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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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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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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Ethynylferrocenyl derivatives of 2,7-acridine (1, 2), 9-N-acridone (4), and 2-anthraquinone (6) are described. (Z)-10-(2-iodo-1-ethenylferrocene)-9(10H)-acridinone (3), an intermediate in the formation of 4, N-Fc(CH2)n-acridone (5; n = 8, 11), 1-Fc-anthraquinone (7), and (E)-(2-FcC=C)-anthraquinone (8) were also investigated. The X-ray structures of 3 and 6 were determined. B3LYP calculations, UV/vis spectroelectrochemistry, cyclic voltammetry, and ESR spectra were used to probe the ground and excited states of both the neutral and oxidized compounds. Emission is observed from oxidized, but not neutral, 4 and 6; however, 1, 2, and 8 are fluorescent. Surprisingly, emission is reduced upon oxidation of 2 and 8, which appears to correlate with the greater distortion in the excited compared to ground states.

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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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Convergent synthesis of a redox-stable nonaferrocenyl dendrimer using a tritopic dendron with disrupted conjugation is described.

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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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Treatment of [(PCy3)2Cl2Ru=CH-Ph] (I) with vinylferrocene 1 and 1-ferrocenyl-1,3-butadiene 2 yielded solid products. These new complexes were characterized by 1H NMR, 31P NMR and 13C NMR spectroscopy. X-ray crystal structures of both the complexes have been solved. The crystal structure of II confirmed the assigned structure and revealed existence of two sets of intermolecular C-H-Cl(M) type interactions, viz. (Ru)Cl-H-C(ferrocene) and (Ru)Cl-H-CHCl2. The air-stable, dark solid II is an efficient catalyst for ring-opening metathesis polymerization (ROMP) of cyclopentene, norbornene and cycloocta-1,5-diene. Electrochemical behavior of the complexes clearly reflects electronic communication between two metal centers.

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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