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This chapter summarizes research work showing that electrostatic interactions may have considerable effects on the stability of complexes formed by the cucurbit[n]uril hosts. Focusing primarily on work carried out by the author’s research group with the cucurbit[7]uril (CB[7]) molecular receptor, this review highlights the role played by electrostatic interactions involving the host cavity portals, in which considerable negative charge density accumulates due to the carbonyl oxygens lacing the portal rims. Electrostatics are responsible for diminished binding affinities between CB[7] and a number of anionic guests containing one or more carboxylate groups. These electrostatic interactions can be used effectively to control the average location of CB[7] along axle-type guests having terminal -COOH groups as a function of their state of protonation, leading to switchable pseudorotaxane systems. They can also be utilized to advantage to develop favorable lateral interactions between CB[7] and other molecular receptors, which results in systems showing cooperative self-assembly.

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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 novel photoelectrochemical cell consisting of a set of organic thin films which generate photocurrents in opposite directions was fabricated. The polythiophene film containing 5,10,15,20-tetraphenylporphyrin (TPP) and fullerene (C60) generated anodic photocurrents in the presence of ferrocene, while that containing TPP alone generated cathodic photocurrents under aerobic condition. The combination of these two film-modified electrodes showed a better cell performance than the simple sum of these two independent photoelectrochemical cells. A push-pull type, double-driven photoelectrochemical cell is proposed in this paper.

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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 series of ferrocenyl ended dendrons containing pi-conjugated systems were obtained using Wittig and Heck reactions. The dendrons were attached to eight functionalized resorcinarenes via Williamson reaction obtaining high molecular weight dendrimers. No electronic communication between metal centers was observed by cyclic voltammetry. All the dendrimers were characterized by 1H, 13C NMR, FTIR, UV-Vis, MALDI-TOF, elemental analyses, and electrochemical studies.

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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 catalytic asymmetric construction of silicon-stereogenic silanes is of great interest and significance, but has met with only limited success to date. We herein report the enantioselective hydrosilylation of alkenes with dihydrosilanes by a chiral half-sandwich scandium catalyst, which constitutes an efficient and general route for the synthesis of a wide range of enantioenriched silicon-stereogenic silanes from easily accessible starting materials. This reaction features a broad substrate scope, high yields, and high enantioselectivity. Some of the chiral tertiary silane products were also converted into valuable derivatives, such as chiral silanol, quaternary silane, and benzosilole 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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A variety of alkenylcarbene complexes [Cp'(CO)2Mn= C(OEt)CH=CHR] (3) (Cp’ = TiS-MeCsH4) was obtained in a straightforward manner upon aldol condensation of [Cp'(CO)2Mn=C(OEt)CH3] (1) with aromatic and alpha,beta- unsaturated aldehydes RC(H)O (2). The reaction is totally stereoselective, giving (E)- or (all-E)-alkenylcarbenes only. The protonation of 3 at low temperature followed by reaction with water affords the alpha,beta-unsaturated aldehyde complexes [Cp'(CO)2Mn(n2-RCH=CHCHO] (5), from which the aldehydes RC(H)=C(H)C(H)O (6) were displaced by acetonitrile. The intermediate aldehyde complexes are shown to result from the hydrolysis of a transient cationic pi- allyl species [Cp'(CO)2Mn(n3-RCHCHC(OEt)H]+ ([4]+) formed upon protonation of 3.

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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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Lysosomally accumulated substances that release a nitroxy group, or a short chain fatty acid or a product of anaerobic metabolism or a thiol or a sulfide often from an ester or similar labile linkage have anti-inflammatory, anti-cancer and anti-bacterial activity. They are useful in treating infectious, inflammatory and malignant disease.

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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 deprotection of the tert-butyl group of a ferrocenyl uracil Peptide Nucleic Acid (PNA) monomer, Fmoc-aeg(R)-OtBu (1) was achieved using a two step synthesis involving hydrolysis in basic conditions to give first the zwitterion of +NH3-aeg(R)-O- (7). Compound 7 was reacted in situ with N-(9-fluorenylmethoxycarbonyloxy)succinimide to obtain the expected compound Fmoc-aeg(R)-OH (2) (Abbreviations: Aeg = (2-aminoethyl)-glycine; Fmoc = 9-fluorenylmethoxycarbonyl; OtBu = tert-butyl; R = 5-(N-ferroce-nylmethylbenzamido)uracyl). Crown Copyright

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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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An improved, short and efficient synthesis of vinylferrocene is reported. This three-step synthesis includes Friedel-Crafts acylation, reduction, and a one-pot mesylation/elimination step to afford the target compound in 62% yield over three steps.

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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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In the present ?genomic era? and in the developing world of DNA chips, DNA detection based on intercalation of specific molecules is of particular interest because the detection process is largely independent of the sequence of the target DNA. In this work, an acridine-orange-based intercalation compound, which was tethered to deglycosylated glucose oxidase was synthesized ad hoc and investigated for its ability to interact with dsDNA. Amperometric detection of DNA hybridization was achieved by signal amplification based on the catalytic oxidation of glucose by DNA-bound glucose oxidase. A clear distinction between dsDNA and ssDNA was achieved by careful design of a DNA-modified electrode surface and prevention of nonspecific adsorption of the acridine-orange-modified enzyme by implementing a potential-assisted immobilization method.

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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 synthesis of para-substituted ferrocene analogues of stilbene was performed by using the Heck reaction, starting from vinylferrocene. The variation of the electronic density of these compounds with the electronic withdrawing strength of the substituents was studied using 13C NMR spectroscopy, absorption spectra and cyclic voltammetry. The correlation of Hammett constants with the redox properties of the substituted compounds using Nagy’s method allowed us to revisit the determination of the Hammett constants of diethyl phosphonate ester and phosphonic acid substituents. Our measurements were in agreement with the literature except for the diethyl phosphonate group.

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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