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Moesbauer parameters are reported for a series of diacetylferrocene (DAF) complexes with Lewis acids (AlCl3, SnCl4, FeCl3, TiCl4).All the complexes show a lowering of quadrupole splitting (QS) relative to uncomplexed DAF.The decreases in QS are discussed in terms of their stereochemistry and related to previous findings in the ferrocenyl ketone series. 119Sn Moessbauer data are presented for SnCl4 * DAF.

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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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Phospholipase D (Pld) Is A Useful Enzyme For Its Transphosphatidylation Activity, Which Enables The Enzymatic Synthesis Of Various Phospholipids (Pls). Many Reports Exist On Pld-Mediated Synthesis Of Natural And Tailor-Made Pls With Functional Head Groups, From Easily Available Lecithin Or Phosphatidylcholine. Early Studies On Pld-Mediated Synthesis Mainly Employed Enzymes Of Plant Origin, Which Were Later Supplanted By Ones From Microorganisms, Especially Actinomycetes. Many Plds Are Members Of The Pld Superfamily, Having One Or Two Copies Of A Signature Sequence, Hxkxxxxd Or Hkd Motif, In The Primary Structures. Pld Superfamily Members Share A Common Core Structure, And Thereby, A Common Catalytic Mechanism. The Catalysis Proceeds Via Two-Step Reaction With The Formation Of Phosphatidyl-Enzyme Intermediate. Both Of The Two Catalytic His Residues Are Critical In The Reaction Course, Where One Acts As A Nucleophile, While The Other Functions As A General Acid/Base. Pld Is Being Engineered To Improve Its Activity And Stability, Alter Head Group Specificity And Further Identify Catalytically Important Residues. Since The Knowledge On Pld Enzymology Is Constantly Expanding, This Review Focuses On Recent Advances In The Field, Regarding Pld-Catalyzed Synthesis Of Bioactive Pls, Deeper Understanding Of Substrate Recognition And Binding Mechanism, Altering Substrate Specificity, And Improving Thermostability. We Introduced Some Of Our Recent Results In Combination With Existing Facts To Further Deepen The Story On The Nature Of This Useful Enzyme.

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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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Ferrocenyl-chalcones and their bichalcone analogues were characterized by IR and NMR spectroscopy, as well as electrochemically. Their UV?visible spectra were recorded, and the electronic transitions were assigned by time-dependent DFT calculations. The single-crystal X-ray structures were determined for two ferrocenyl bichalcones.

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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 substitution reaction of ferrocenyl alcohol with various nucleophiles catalyzed by cerium ammonium nitrate (CAN) was investigated. This CAN-mediated direct carbon-carbon bond formation provides the corresponding products in moderate to high yields with relatively lower catalyst loading (5 mol %) at room temperature. It demonstrated a convenient synthetic protocol for the ferrocene functionalities. Crown 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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tetraphenylcyclobutadienecobalt(I) reacts with lithium tetrachloropalladate(II) in the presence of sodium acetate to give an ortho-palladated binuclear complex.The ?-bonded structure of the complex was confirmed by studies of the IR and 1H-NMR spectra and of the reactions with triphenylphosphine, thalium(I) acetylacetonate, and lithium aluminum deuteride.The reactions of the ?-bonded complex with carbon monoxide and olefins have been examined.

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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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Novel ferrocenyl dendrimers with ferrocene as a surface group and with triazole as a bridging unit have been synthesised through click chemistry. The increasing numbers of triazole and ferrocenyl units at the antenna increase the light absorbing ability. The electrochemical behaviour changes with increasing ferrocenyl and triazole units.

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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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(Chemical Equation Presented). A simple, highly efficient, and general strategy for the direct synthesis of amino-(N-alkyl)benzenesulfonamides has been accomplished via direct N-alkylation of aminobenzenesulfonamides bearing both different types of amino groups with alcohols as alkylating agents. Notably, this research exhibited the potential for the recognition of different types of amino groups in the N-alkylation of complex molecules with alcohols, facilitating the progress of the transition-metal-catalyzed “hydrogen autotransfer (or hydrogen-borrowing) process.”

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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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alpha-Ferrocenylcarbinols, readily obtained by direct condensation of aldehydes or ketones with ferrocene, react smoothly with mercaptosuccinic acid to give ferrocenylmethylthiosuccinic acids.The optically active dimethyl (R)-mercaptosuccinate provides a way for the resolution of tertiary alcohols.

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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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MicroRNAs (MiRNAs) have been regarded as clinically important biomarkers and drug discovery targets. In this work, we reported a simple and ultrasensitive electrochemical method for miRNAs detection based on single enzyme amplification and electrochemical-chemical-chemical (ECC) redox cycling. Specifically, upon contact with the target miRNAs, the hairpin structure of biotinylated DNA immobilized on gold electrode was destroyed and the biotin group in DNA was forced away from the electrode surface, allowing for the coupling of streptavidin-conjugated alkaline phosphatase (SA-ALP). Then, ascorbic acid (AA, the enzymatic product of ALP) triggered the ECC redox cycling with ferrocene methanol (FcM) and tris(2-carboxyethyl)phosphine (TCEP) as the redox mediator and the chemical reducing reagent, respectively. The method was more sensitive than that with horseradish peroxidase (HRP) or glucose oxidase (GOx) triggered recycling since one ALP molecule captured by one target miRNA molecule promoted the production of thousands of AA. Analytical merits (e.g., detection limit, dynamic range, specificity, regeneration and reproducibility) were evaluated. The feasibility of the method for analysis of miRNA-21 in human serum has also been demonstrated.

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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 alpha-ferrocenylalkyl carbenium ions are formed from ferrocene and carbonyl compounds in strongly acidic media, in particular mixtures of fluorosulfuric acid and trichloroacetic acid.The alpha-ferrocenylalkyl carbenium ions are scavenged by nucleophiles or bases.The addition of nucleophiles produces the corresponding alpha-substituted ferrocenyl alkanes.Proton abstraction by base from the beta-position leads to the ferrocenylethene derivatives.Such electrophilic substitutions of ferrocene by carbonyl compounds, followed by suitable scavengeing of the alpha-ferrocenylalkyl carbenium ion, form the basis of one-pot syntheses of various ferrocene derivatives.

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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