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Mobile species transfer accompanying the redox switching of poly(vinylferrocene) (PVF) in aqueous perchlorate solutions of four cations was investigated using the electrochemical quartz crystal microbalance (EQCM). Cyclic voltammetry in 0.05 M solutions containing hydronium, sodium, rubidium or tetraethylammonium cation was employed. The mass transients could not be explained solely in terms of anion and solvent transport processes. EQCM transient data showed that the cation as well as perchlorate and water transport participated in the redox switching process in the four bathing solutions. Results and interpretation of the experimental approach are presented.

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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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Multicomponent reactions are fundamentally different from two-component reactions, as multicomponent reactions can enable the efficient and step-economical construction of complex molecular scaffolds from simple precursors. Here, an unprecedented three-component direct C-H addition was achieved in the challenging meta-selective fashion. Fluoroalkyl halides and a wide range of alkenes, including vinylarenes, unactivated alkenes, and internal alkenes, were employed as the coupling partners of arenes in this strategy. The detailed mechanism presented is supported by kinetic isotope studies, radical clock experiments, and density functional theory calculations. Moreover, this strategy provided access to various fluoride-containing bioactive 1,1-diarylalkanes and other challenging synthetically potential products.

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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 aminocarbonylation of alkenes is a powerful method for accessing the beta-amino carbonyl motif that remains underdeveloped. Herein, the development of intermolecular aminocarbonylation reactivity of iminoisocyanates with alkenes is presented. This includes the discovery of a fluorenone-derived reagent, which was effective for many alkene classes and facilitated derivatization. Electron-rich substrates were most reactive, and this indicated that the LUMO of the iminoisocyanate is reacting with the HOMO of the alkene. Computational and experimental results support a concerted asynchronous [3 + 2] cycloaddition involving an iminoisocyanate, which was observed for the first time by FTIR under the reaction conditions. The products of this reaction are complex azomethine imines, which are precursors to valuable beta-amino carbonyl compounds such as beta-amino amides and esters, pyrazolones, and bicyclic pyrazolidinones. A kinetic resolution of the azomethine imines by enantioselective reduction (s = 13.43) allows access to enantioenriched products. Overall, this work provides a new tool to convert alkenes into beta-amino carbonyl compounds.

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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 emergence of resistance against existing antileishmanial drugs necessitates the search for new classes of antileishmanial compounds. Herein a series of structurally diverse ferrocenylquinolines have been synthesized and evaluated for in vitro antileishmanial activity against Leishmania donovani using the MTT assay. Thirteen (M2-M14) substituted ferrocenylquinoline congeners possessing triazole rings were generated by palladium mediated Suzuki-Miyaura coupling reaction of 5-iodoferrocenylquinolinetriazole and substituted arylboronic acids. All the synthesized compounds were tested for its antileishmanial activity using both promastigote and amastigote stages of L. donovani. Among them, three compounds (M4, M7 and M9) exhibited promising anti-promastigote activity, with an IC50value of 28.7 muM, 22.1 muM and 28 muM, respectively, and no cytotoxicity toward host splenocytes. These three compounds are equally effective against the intracellular amastigote stage of L. donovani showing the IC50values of 16 muM (M4), 8 muM (M7) and 16 muM (M9), respectively, with consistent nitric oxide generation as required for parasite clearance. From the battery of tests conducted in this study, it appears that these compounds induce parasite death by promoting cell cycle arrest and triggering apoptosis.

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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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We introduce a three-way molecular motion which can be a suitable switching system in future molecule-based nanocircuits. A real-space investigation revealed that vinylferrocene adsorbs site-specifically on the Ge(100) surface and then shows a reversible tilting motion, similar to a seesaw. Unlike conventional molecular motions, it not only has three stable switching states at room temperature but also shows a motion-induced surface-structure modification, allowing surface-mediated signal transmission. Demonstrated STM-tip influence on the motion allows the feasibility of tip-induced manipulation.

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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 two related compounds (R = OEt or ferrocenyl C5H4FeC5H5, Fc), have been prepared, the first by insertion of ethyl ethynyl ether (CH<*>COEt) into and the second by oxidative addition of ethenylferrocene (CH2 = CHFc) to respectively.Spectroscopically both compounds are similar to known related compounds with alkyl- or aryl-substituted vinyl ligands.A single-crystal X-ray structural study of each was made in an attempt to detect any structural effects of ?-donation by the substituents at the vinylgroup, such as was observed for .The latter compound has been shown to have a zwitterionic structure with an alkylidene bridge between two osmium atoms rather than the normal mu,eta2-vinyl mode of bonding.The two compounds studied here have essentially normal mu,eta2-vinyl bridges, but with some distortion towards the alkylidene bonding type, more pronounced for R = OEt.

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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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An efficient Rh(III)-catalyzed oxidative olefination by directed C-H bond activation of N-methoxybenzamides is reported. In this mild, practical, selective, and high-yielding process, the N-O bond acts as an internal oxidant. In addition, simply changing the substituent of the directing/oxidizing group results in the selective formation of valuable tetrahydroisoquinolinone products.

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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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Amongst the halogens, the involvement of bromine atoms in various types of intermolecular interactions is comparatively the least studied. In this manuscript, we report the formation of C[sbnd]Br?pi interactions, with the pi-rings being the cyclopentadienyl (Cp) rings of a ferrocene molecule in a newly synthesized compound (E)-1,3-dibromo-5-(2-(ferrocenyl)vinyl)benzene. We have also performed a detailed quantitative analysis on C[sbnd]Br?pi interactions observed in the synthesized molecule and in several related molecules found in the Cambridge Structure Database (CSD) showing the presence of these interactions. A topological analysis based upon QTAIM theory and electrostatic potential ESP mapped on the Hirshfeld surface of these molecules confirm that these interactions are better described as ?halogen bonds? wherein the electropositive region (sigma-hole) on the Br-atom interacts with the electronegative region over the Cp-ring of the ferrocene. Further, the electronegative region on the bromine atom (perpendicular to the C[sbnd]Br bond) was observed to be involved in the formation of highly directional C[sbnd]H?Br interactions with the ?C[sbnd]Br?H close to 90. Thus the bromine atom is acting as both a ?halogen bond donor? and ?hydrogen bond acceptor? in the crystal packing with the two interactions being mutually orthogonal.

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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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Four first- and second-generation heterometallic ferrocenyl derived p-cymene-Ru(II) metallodendrimers, of general formula [DAB-PPI{(kappa6-p-cymene)Ru((C7H5NO)-2-N,O)PTA(5-ferrocenylvinyl)}n][PF6]n and [DAB-PPI{(kappa6-p-cymene)Ru((C6H5N2)-2-N,N)Cl(5-ferrocenylvinyl)}n][PF6]n (where n = 4 (G1), 8 (G2), DAB = 1,4-diaminobutane, PPI = poly(propyleneimine), PTA = 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane) have been synthesized. All complexes have been characterized using analytical (i.e., HR-ESI mass spectrometry, HPLC, elemental analysis, and cyclic voltammetry) and spectroscopic (i.e., 1H and 13C{1H} NMR and infrared) methods. Electrochemical studies reveal that the N,O-p-cymene-Ru(II)-PTA complexes result in two irreversible redox processes (oxidation of the Fe(II) and Ru(II) centers), while the N,N-p-cymene-Ru(II) complexes display one reversible wave (Fe(II)/Fe(III) couple). Heterometallic model complexes have been prepared, and for one of the complexes, its molecular structure has been determined by single-crystal X-ray crystallography. In vitro antiproliferation activity of the dendritic ligands and their complexes were evaluated against A2780 and A2780cisR human ovarian cancer lines, the SISO human cervix cancer line, the LCLC-103H human lung cancer line, and the 5637 human bladder cancer line. Nine of the twelve compounds slowed the growth of the ovarian cancer cell lines by more than 50% at equi-iron concentrations of 5 muM.

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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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2-Vinylpyridines undergo regioselective beta-alkylation with alkenes in the presence of a rhodium(I) complex as a catalyst to give products resulting from an anti-Markownikoff reaction. These results show the feasibility of alkylation of an alkenic position as a result of C-H bond activation. 2-(Prop-1-en-2-yl)pyridine 1 and 1-phenyl-1-(2-pyridyl)ethylene 15 react with linear terminal alkenes to give the corresponding alkylated products in high yields. Cyclic alkenes, allyl alcohol, but-3-en-1-ol and methyl vinyl ketone, however, fail to react with 1. Pent-2-ene gives the linear alkylated product in low yield. 6-Methyl-2-vinylpyridine 24 and 2-vinylpyridine 32 give the alkylated products in low yield together with their dimeric products. The alkenic C-H bond of 2-(cyclohex-1-enyl)pyridine 36 has been regioselectively alkylated. 2-(Cyclohex-1-enyl)pyridine 36 with alkenes in the presence of the RhI catalyst undergoes regiospecific alkylation at the alkenic position.

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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