Archives for Chemistry Experiments of 1271-51-8

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A tunable route for the synthesis of azomethine imines and beta-aminocarbonyl compounds from alkenes

Cyclic azomethine imines possessing a beta-aminocarbonyl motif are accessed from simple alkene and hydrazone starting materials. A thermal, concerted alkene aminocarbonylation pathway involving an imino-isocyanate intermediate is proposed and supported by DFT calculations. A notable feature of the process is the steric shielding present in the dipoles formed, which allows for facile purification of the products by chromatography or crystallization. In addition, a fluorenone-derived reagent is reported, which provides reactivity with several alkene classes and allows for mild derivatization of the dipoles into beta-aminoamides, beta-aminoesters, and beta-amino acids.

A tunable route for the synthesis of azomethine imines and beta-aminocarbonyl compounds from alkenes

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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

 

The important role of Vinylferrocene

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X-ray absorption studies of poly(vinylferrocene) polymers for anion separation

X-ray absorption spectroscopy (XAS) was used to study the electrochemical incorporation of perrhenate anion, from a 0.1 M NH4ReO4 solution, into poly(vinylferrocene) (PVFc) and a modified PVFc (a copolymer of 30% t-butyl acetylferrocene and 70% t-butyl divinyl ferrocene). The polymers were deposited on a carbon cloth current collector from a solution of the polymers in CH2Cl2. In situ XAS measurements were done at the Fe K edge on the reduced polymers and at 0.9 V vs. Ag/AgCl. Ex situ XAS was done at the Re L3 edge after oxidation of the polymers at 0.9 V. The oxidized electrodes were washed in water to remove dissolved NH4ReO4 in the electrode pores. XAS was done both on wet-washed electrodes and on electrodes that were dried. XAS showed that at 0.9 V the Fe was oxidized from a ferrocene to a ferrocenium moiety and the Fe-C bond distance increased from 2.05 to 2.08 A. Both the X-ray absorption near-edge spectroscopy and extended X-ray absorption fine structure (EXAFS) results are consistent with having >75% of the ferrocene moieties in the polymer oxidized at 0.9 V. The Fe K-edge EXAFS showed no direct indication of interaction of Fe with ReO4-. At the Re L3 edge the only indication of interaction of ReO4- with the polymers was a slight change in the XANES features.

X-ray absorption studies of poly(vinylferrocene) polymers for anion separation

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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

 

Properties and Exciting Facts About Vinylferrocene

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Preparation and X-Ray Crystal-structure Determinations of Structural Isomers of Ferrocenyl-substituted Dihydrofurans

The reaction of tris(3-iodopentane-2,4-dionato)cobalt(III) with vinylferrocene in the presence of triphenylphosphine and a catalytic amount of PdII produced two structural isomers.The characterisation of these isomers, 2- and 3-ferrocenyl-4-acetyl-2,3-dihydro-5-methylfuran <(B) and (C), respectively> is described.Their structures have been determined by single-crystal X-ray diffractometry: (B) is orthorhombic, space group Pbca with a=9.821(2), b=10.414(4), c=27.761(6) Angstroem, final R=0.031, R’=0.050 for 1706 reflections; (C) is monoclinic, space group is P21/c with a=9.692(1), b=7.678(5), c=19.082(3) Angstroem, final R=0.031, R’=0.048 for 1641 reflections.

Preparation and X-Ray Crystal-structure Determinations of Structural Isomers of Ferrocenyl-substituted Dihydrofurans

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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

 

Brief introduction of Vinylferrocene

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Intermolecular aminocarbonylation of alkenes using concerted cycloadditions of iminoisocyanates

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.

Intermolecular aminocarbonylation of alkenes using concerted cycloadditions of iminoisocyanates

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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

 

Simple exploration of 1271-51-8

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beta-Ferrocenyl-beta-amino alcohols: a new class of central chiral ferrocene derivatives

An efficient procedure for the enantioselective synthesis of beta-ferrocenyl-beta-amino alcohols, a new class of central chiral ferrocene derivatives suitable for the elaboration of auxiliaries and ligands for asymmetric synthesis, is described. Key steps of the method are the catalytic asymmetric dihydroxylation of 1-ferrocenyl alkenes and the regio- and stereoselective azide substitution of the hydroxyl group adjacent to the ferrocene moiety. The stereochemistry of the substitution step has been established by X-ray diffraction analysis of a cyclic derivative. The first catalytic enantioselective synthesis of a beta-ferrocenyl-beta-amino acid derivative is also disclosed.

beta-Ferrocenyl-beta-amino alcohols: a new class of central chiral ferrocene derivatives

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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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Electric Literature of 1271-51-8, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.1271-51-8, Name is Vinylferrocene, molecular formula is C12H3Fe. In a article£¬once mentioned of 1271-51-8

alpha-ferrocenylalkylation of 1,5-disubstituted tetrazoles and certain transformations of reaction products

The reaction of alpha-hydroxyferrocenylalkyl derivatives and vinylferrocene with 1,5-disubstituted tetrazoles in methylene chloride-aqueous acid HX (X = BF4, ClO4) two-phase systems gives a mixture of 1,3,5- and 1,4,5-trisubstituted tetrazolium salts, the fraction of the 1,3,5-isomers prevailing. The synthesized salts are readily dealkylated under the action of bases to give the above starting compounds. Heating of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium and 3(4)-(ferrocenylmethylene)-2-methyl-1-phenyltetrazolium tetrafluoroborates in anhydrous methanol or ethanol in the presence of catalytic amounts of alkali gives rise to ferrocenylcarbinol ethers. Other nuclephiles (pyridine, triphenylphosphine, sodium thiocyanate, sodium p-toluenesulfinate, dibenzoylmethane) also react with the above tetrazolium salts, forming ferrocenylmethylation products. Heating of equimolar amounts of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium or 3(4)- (ferrocenylmethylene)-2-methyl-1-phenyltetrazolium perchlorates with mercury(II) perchlorates in anhydrous ethanol results in mercuration of the starting tetrazolium salts, involving hydrogen substitution in the methylene or methyl groups bound to tetrazolium carbon atoms. The condensation of the same salts with p-N,N-(dimethylamino)nitrosobenzene, leading to azomethine formation, occurs under similar conditions.

alpha-ferrocenylalkylation of 1,5-disubstituted tetrazoles and certain transformations of reaction 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

 

Extracurricular laboratory:new discovery of Vinylferrocene

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(Planar-Chiral) Ferrocenylmethanols: From Anionic Homo Phospho-Fries Rearrangements to alpha-Ferrocenyl Carbenium Ions

The reaction of FcCH2OH with chlorophosphates gave ferrocenyl phosphates FcCH2OP(O)(OR)2 [Fc = Fe(eta5-C5H5)(eta4-C5H4)], which readily separate into phosphate anions and ferrocenyl carbo-cations. The latter species undergoes consecutive reactions, for example, electrophilic aromatic substitutions. When nitriles, instead of alcohols, are treated with FcLi or tBuLi and chlorophosphates, chiral-pool based ferrocenylimino phosphoramidates Fc-CR=N-P(O)(OR*)2 are formed, which are promising candidates for anionic homo phospho-Fries rearrangements. Moreover, the sterically demanding chiral chlorophosphate with R* enabled oxidative couplings of the imines to form a diferrocenylazine. Similarly, the reaction of Fc?Li with 9-anthrylnitrile produced a 10-ferrocenyl-substituted product, contrary to a reaction at the C?N functionality. A planar-chiral ortho-P(S)Ph2-functionalized ferrocenylmethanol also gave carbo-cations under acidic conditions. These species can be sulfurized in a unique way giving thio ethers, whereby the in situ formed 1,2-P(S)Ph2,CH2+ ferrocene cation acts as the sulfur and electron source. However, lowering the substrate concentration prevents sulfur migration, resulting in electrophilic substitution reactions with aromatic solvents. Planar-chiral ferrocenylmethyl thio or anisyl derivatives were applied as ligands in Pd-catalyzed Suzuki?Miyaura C,C cross-couplings for the atroposelective synthesis of hindered biaryls with up to 26 % ee at low catalyst loadings (1 mol-% Pd).

(Planar-Chiral) Ferrocenylmethanols: From Anionic Homo Phospho-Fries Rearrangements to alpha-Ferrocenyl Carbenium Ions

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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

 

Simple exploration of Vinylferrocene

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Synthetic Route of 1271-51-8, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.1271-51-8, Name is Vinylferrocene, molecular formula is C12H3Fe. In a article£¬once mentioned of 1271-51-8

Polarizability of ferrocene derivatives from quantum mechanical delta-function potentials

The atomic bond and molecular polarizabilities of some ferrocene derivatives have been calculated using variational method and delta-function electronic wave functions.Scales have been presented, where the derivatives are classified in order of their polarization properties.Common trends and patterns of behaviour are recognized and discussed.

Polarizability of ferrocene derivatives from quantum mechanical delta-function potentials

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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

 

Final Thoughts on Chemistry for 1271-51-8

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Application of 1271-51-8, Chemistry is the science of change. But why do chemical reactions take place? Why do chemicals react with each other? The answer is in thermodynamics and kinetics.In a document type is Article, and a compound is mentioned, 1271-51-8, Vinylferrocene, introducing its new discovery.

Radical Acylfluoroalkylation of Olefins through N-Heterocyclic Carbene Organocatalysis

Fluorinated ketones are widely prevalent in numerous biologically interesting molecules, and the development of novel transformations to access these structures is an important task in organic synthesis. Herein, we report the multicomponent radical acylfluoroalkylation of a variety of olefins in the presence of various commercially available aromatic aldehydes and fluoroalkyl reagents through N-heterocyclic carbene organocatalysis. With this protocol, over 120 examples of functionalized ketones with diverse fluorine substituents have been synthesized in up to 99 % yield with complete regioselectivity. The generality of this catalytic strategy was further highlighted by its successful application in the late-stage functionalization of pharmaceutical skeletons. Excellent diastereoselectivity could be achieved in the reactions forging multiple stereocenters. In addition, preliminary results have been achieved on the catalytic asymmetric variant of the olefin difunctionalization process.

Radical Acylfluoroalkylation of Olefins through N-Heterocyclic Carbene Organocatalysis

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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

 

The Absolute Best Science Experiment for Vinylferrocene

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Combined electrochemical and radiotracer study on the ionic charge transport coupled to electron transfer and ionic equilibria in electroactive polymer films on electrodes

A combination of electrochemical and radiotracer methods offers a unique possibility of studying the motion of counter- and co-ions during electrochemical transformations occurring in a polymer film. In addition, information can be obtained about the embedding of electrolytes during electropolymerization penetration of electrolytes into the films prepared by solvent-evaporation procedures, the ion-exchange behavior, and the mechanism of the redox processes. Results on poly/vinyl ferrocene/tetracyanoquinodimethane polyester, polypyrrole, and polyaniline are described.

Combined electrochemical and radiotracer study on the ionic charge transport coupled to electron transfer and ionic equilibria in electroactive polymer films on electrodes

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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