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1-Ferrocenylcyclopropene and 1-ferrocenylcyclopropyl cation

Dehydrobromination of cis and trans isomers of 1-bromo-2-ferrocenylcyclopropanes affords 1-ferrocenylcyclopropene. Its protonation with HBF4 results in 1-ferrocenylcyclopropylium tetrafluoroborate, which alkylates N,N-dimethylaniline in para position to yield 1-(p-dimethylaminophenyl)-1-ferrocenylcyclopropane. 1-Ferrocenylcyclopropene reacts with 1,3-diphenylisobenzofuran to give the classical [4+2]-cycloaddition product. Its structure as exo-2-ferrocenyl-1,5-diphenyl-6,7-benzo-8-oxatricyclo [3.2.1.02.4]oct-6-ene was established based on the data from X-ray diffraction analysis.

1-Ferrocenylcyclopropene and 1-ferrocenylcyclopropyl cation

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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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Kinetics of the synthesis of the S-(1-ferrocenylethyl)thioglycolic acid

A systematic study of the reactions of a number of alpha-hydroxylated ferrocene derivatives with thioglycolic acid confirms that the reaction is extremely fast, viz., 15-20 min <1>, as compared with earlier procedures (12 h) <2,3>.The important kinetic parameters of the reaction of 1-ferrocenylethanol with the thioglycolic acid in the presence of trifluoroacetic acid have been determined.

Kinetics of the synthesis of the S-(1-ferrocenylethyl)thioglycolic acid

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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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Efficient thiol-yne click chemistry of redox-active ethynylferrocene

The application of ethynylferrocene, FcCCH (1), as a highly efficient electroactive precursor for the thiol-yne click reaction is presented. For this purpose, a wide range of functionalized thiols, namely 2-mercaptoethanol, 1-thioglycerol, 3-mercaptopropionic acid, 4-aminothiophenol, and benzene-1,3-dithiol as well as tetrathiol pentaerythritol tetrakis(3-mercaptopropionate), were investigated. This facile thiol-ethynylferrocene radical reaction has resulted in the quantitative formation and isolation of the newly ferrocenyl-vinyl sulfides FcCH=CHS(CH2)2OH (2Z and 2E), FcCH=CHSCH2CH(OH)CH2OH (3Z and 3E), FcCH=CHS(CH2)2COOH (4Z and 4E), FcC(CH2)S(1,4-C6H4)NH2 (5alpha), FcCH=CHS(1,3-C6H4)SCH=CHFc (6), and [FcCH=CHS(CH2)2COOCH2]4C (7). Thiol-ethynylferrocene reactions have been initiated either by heat, in toluene with AIBN, or by UV light irradiation in THF in the presence of DMPA as photoinitiator. The outcome of the hydrothiolation of ethynylferrocene strongly depends on the thiol structure and on the initiation method employed. A simple mixing of metallocene 1 with the thiol HS(CH2)2OH or HS(CH2)2COOH in a proper ratio, in THF at 20 C, in a initiator-free thiol-yne reaction, causes hydrothiolation of 1 to occur, allowing for the formation of vinyl sulfides 2Z, 2E and 4Z, 4E in good isolated yields. In contrast to the bis-addition typically observed for thiol-yne reactions, no double hydrothiolation to FcCCH has been observed for any of the thiols under any conditions studied. Electrochemical studies showed that tetrametallic compound 7, containing four sulfur-bridged ferrocenyl-vinyl moieties, behaves as a tetrapodal adsorbate molecule, exhibiting excellent chemisorption properties, and spontaneously forms robustly adsorbed 7 films onto Au or Pt electrode surfaces.

Efficient thiol-yne click chemistry of redox-active ethynylferrocene

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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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Reactions of Cp2TiMe2 with ferrocene and (n5-Cp)Co(n4-C4Ph4) derived esters and amides: A new route for 1-methylvinyl and methyl ketone derived metal sandwich compounds

Reactions of Cp2TiMe2, with the ester derivatives of organometallic sandwich compounds (n5-RC5H4)Fe(n5-C5H5) and (n5-RC5H4)Co(n4-C4Ph4) (R=ester groups) gave products having R=C(CH2)Me, instead of the expected vinyl ethers indicating conversion of the ester units by Cp2TiMe2 to methyl ketones followed by methylenation. A reaction of Cp2TiMe2 with the diester (n5-RC5H4)Co(n4-C4Ph3R)(R=C(O)OMe) also gave similar results. The study has also been successfully extended to metal sandwich derived amides, thio and seleno esters. By controlling the amount of Cp2TiMe2, the reactions were also stopped at the methyl ketone stage and the methyl ketones were isolated in good yields and characterized. The method provides an easy and direct access to convert organometallic sandwich derived esters and related compounds to 1-methylvinyl derived products.

Reactions of Cp2TiMe2 with ferrocene and (n5-Cp)Co(n4-C4Ph4) derived esters and amides: A new route for 1-methylvinyl and methyl ketone derived metal sandwich compounds

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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

 

Archives for Chemistry Experiments of Vinylferrocene

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H2-Acceptorless Dehydrogenative Boration and Transfer Boration of Alkenes Enabled by Zirconium Catalyst

The first example of an efficient and direct dehydrogenative boration of alkenes for vinyl boronate ester synthesis was achieved using a zirconium catalyst. Our methodology avoids using precious transition metals, additional hydrogen acceptors, high temperatures, and long reaction times, which were required to overcome the reducing ability of borane, to give alkyl boronate esters. Detailed mechanistic studies revealed a reversible reaction pathway and further suggested applying the zirconium complex as a ?shuttle catalyst? for transfer boration, which thus sidesteps the use of relatively sensitive borane.

H2-Acceptorless Dehydrogenative Boration and Transfer Boration of Alkenes Enabled by Zirconium Catalyst

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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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One of the major reasons for studying chemical kinetics is to use measurements of the macroscopic properties of a system, SDS of cas: 1271-51-8, such as the rate of change in the concentration of reactants or products with time.In a article, mentioned the application of 1271-51-8, Name is Vinylferrocene, molecular formula is C12H3Fe

Substituent effects of 1,2-dithiole groups on the electrochemical oxidation of some ferrocenyl-1,2-dithiole compounds

New ferrocenyl compounds substituted by sulfur containing groups were synthesized leading to ferrocenyl-3H-1,2-dithiole-3-thiones and related compounds. The substituent of the ferrocene was a [3-thioxo-3H-1,2-dithiol]-4 or 5-yl, a [3-oxo-3H-1,2-dithiol]-4 or 5- yl or a [3-methylsulfanyl-3H-1,2-dithiolium]-4 or 5-yl cation group. Their anodic behavior was studied by cyclic voltammetry at a Pt electrode in aprotic solvent. All synthesized ferrocenes exhibited a one-electron reversible oxidation leading to the corresponding ferricinium cation. At low potential scan, the irreversible oxidation of 5-ferrocenyl-3H-1,2-dithiole-3-thione was observed and attributed to a dimerization involving the dithiolethione group. Redox potential of the reversible oxidation allowed the determination of the electronic effect of the 1,2-dithiole groups. The Hammett sigmap constants of the dithiole substituents were obtained from linear correlation between oxidation potentials and electronic effects. The results showed that the [3-thioxo-3H-1,2-dithiol]-5-yl and the [3-methylsulfanyl-3H-1,2-dithiolium]-5-yl cation groups were strong inductive electron withdrawing substituents characterized by sigmap values of 0.55 and 0.97, respectively.

Substituent effects of 1,2-dithiole groups on the electrochemical oxidation of some ferrocenyl-1,2-dithiole compounds

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. SDS of cas: 1271-51-8, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 1271-51-8, in my other articles.

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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 Chemistry of a Non-Interacting Vicinal Frustrated Phosphane/Borane Lewis Pair

The dimesitylphosphinocyclopentene/HB(C6F5)2-derived vicinal trans-1,2-P/B frustrated Lewis pair (FLP) 4 shows no direct phosphane?borane interaction. Toward some reagents it behaves similar to an intermolecular FLP; it cleaves dihydrogen, deprotonates terminal alkynes, and adds to organic carbonyl compounds including CO2. It shows typical intramolecular FLP reaction modes (cooperative 1,1-additions) to mesityl azide, to carbon monoxide, and to NO. The latter reaction yields a persistent P/B FLPNO nitroxide radical, which undergoes H-atom abstraction reactions. The FLP 4 serves as a template for the CO reduction by [HB(C6F5)2] to generate a FLP-eta2-formylborane. The formylborane moiety is removed from the FLP template by reaction with pyridine to yield a genuine pyridine stabilized formylborane that undergoes characteristic borane carbaldehyde reactions (Wittig olefination, imine formation). Most new products were characterized by X-ray diffraction.

The Chemistry of a Non-Interacting Vicinal Frustrated Phosphane/Borane Lewis Pair

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Metathetical reactions of Re(VII) alkylidene-alkylidyne complexes of the type Re(CR?)(CHR?)[OCMe(CF3)2]2 (R? = CMe3 or CMe2Ph) with terminal and internal olefins

1-Decent and methyl 9-decenoate react with syn- and anti-Re(C-t-Bu)(CH-t-Bu)(ORF6) to give syn- and anti-Re(C-t-Bu)[CH(CH2)7Me](ORF6)2 and syn- and anti-Re(C-t-Bu)[CH(CH2)7CO2Me](OR F6)2, respectively (ORF6 = OCMe(CF3)2). The new alkylidene complexes are unstable in the presence of excess terminal olefin and decompose upon attempted isolation. However, vinylferrocene reacts relatively smoothly and reversibly with syn-Re(C-t-Bu)(CH-t-Bu)(ORF6)2 in a noncoordinating solvent to yield tert-butylethylene and primarily anti-Re(C-t-Bu)(CHFc)(ORF6)2 (Fc = ferrocenyl). anti-Re(C-t-Bu)(CHFc)(ORF6)2 (a = 9.769 (2) A, b = 30.746 (7) A, c = 10.140 (2) A, beta = 116.78 (1), V = 2719 (2) A3, space group = P21/a, Z = 4, FW = 815.50, p(calcd) = 1.992 g/cm3, R = 0.052, Rw = 0.050) was shown to be a pseudotetrahedral species with an unusually acute Re=Calpha – Cbeta angle (114.8 (7)) and short Re=C bond (1.70 (1) A). In the presence of THF or dimethoxyethane, complexes of the type syn- or anti-Re(C-t-Bu)(CHR)(ORF6)2S2 (R = Me, Et, Ph; S = THF or 0.5DME) could be prepared in high yield from Re(C-t-Bu)(CH-t-Bu)(ORF6)2 and CH2=CHR. Heteroatom-substituted (O, S, or N) terminal olefins react more rapidly than ordinary olefins with Re(C-t-Bu)(CH-t-Bu)(ORF6)2 in the presence of THF to yield complexes of the type syn- or anti-Re(C-t-Bu)(CHX)(ORF6)2(THF)2 (X = OR, SR, NR2, or p-dimethylaminophenyl). The X-ray structure of syn-Re(C-t-Bu)(CHOEt)(ORF6)2(THF)2 (a = 10.318 (1) A, b = 18.303 (2) A, c = 16.181 (2) A, beta = 96.98 (2), V = 3033 (1) A3, space group = P21/c, Z = 4, FW = 819.74, rho(calcd) = 1.795 g/cm3, R = 0.052, Rw = 0.050) showed it to be a pseudooctahedral complex containing cis alkylidyne and alkylidene ligands and a THF ligand trans to each. The Re-O bond to the THF trans to the neopentylidyne ligand is significantly longer than that trans to the ethoxymethylene ligand; presumably it is the THF ligand trans to the neopentylidyne ligand that exchanges more rapidly with free THF in solution. 2-Pentene or methyl oleate is metathesized in the presence of Re(C-t-Bu)(CH-t-Bu)(ORF6)2, and intermediate alkyidene complexes can be observed in each case. Addition of 3-hexene to Re(C-t-Bu)(CH-t-Bu)(ORF6)2 followed by TMEDA yields Re(C-t-Bu)(CHEt)(ORF6)2(TMEDA). Internal olefins are metathesized only very slowly by Re(C-t-Bu)(CH-t-Bu)(ORF6)2 in the presence of several equivalents of THF or DME or especially in neat THF or DME.

Metathetical reactions of Re(VII) alkylidene-alkylidyne complexes of the type Re(CR?)(CHR?)[OCMe(CF3)2]2 (R? = CMe3 or CMe2Ph) with terminal and internal olefins

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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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Copper-Catalyzed Asymmetric Borylallylation of Vinyl Arenes

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.

Copper-Catalyzed Asymmetric Borylallylation of Vinyl Arenes

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Highly enantioselective synthesis of trifluoromethyl cyclopropanes by using Ru(ii)-Pheox catalysts

An asymmetric synthesis of various trifluoromethyl cyclopropanes from olefins, such as vinyl ferrocene, vinyl ethers, vinyl amines, vinyl carbamates and dienes, was achieved by using Ru(ii)-Pheox catalysts. This catalytic system can function at a low catalyst loading (3 mol%) compared with those reported previously, and the desired cyclopropane products are obtained in high yields with excellent diastereoselectivity (up to >99:1) and enantioselectivity (up to 97% ee).

Highly enantioselective synthesis of trifluoromethyl cyclopropanes by using Ru(ii)-Pheox catalysts

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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