- Stereo- and enantioselectivity in catalytic hydrogenolysis of chiral substituted ferrocenes to give cyclopentanes
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The catalytic hydrogenolysis of 1,2-disubstituted ferrocenes having planar chirality and functional groups such as carboxyl (including ester) or tertiary amino proceeds under mild conditions (1 atm of H2, Pd/C, CF3COOH, 50 deg C) with the retention of fun
- Sokolov, V. I.,Troitskaya, L. L.,Khrushcheva, N. S.,Reutov, O. A.
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- Thermodynamics and molecular dynamics of some ferrocene derivatives
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The heat capacities of acetylferrocene, 1,1′-diacetylferrocene, and 1,1′-diethylferrocene were investigated by low-temperature adiabatic calorimetry in the temperature range from 5 to 300 K and their thermodynamic functions were calculated. The enthalpies
- Domracheva,Karyakin,Sheiman,Kamelova,Larina,Suvorova,Domrachev
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- The reactions of acylferrocenes with samarium diiodide: Reduction, deoxygenation, reductive coupling and rearrangement
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Acylferrocenes reacted with samarium diiodide in the presence of water to give the corresponding (α-hydroxyalkyl)ferrocenes or alkylferrocenes depending on the reaction time and temperature. On treatment with samarium diiodide in the absence of water, ferrocenecarbaldehyde underwent a reductive coupling to give pinacols, whereas acetylferrocene yielded 3,3-diferrocenyl-2-butanone and 2,3-diferrocenyl-2-butene via the subsequent rearrangement and deoxygenation.
- Jong, Shean-Jeng,Fang, Jim-Min,Lin, Chun-Hsu
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- Simple reduction of ferrocenyl aldehydes and ketones by sodium boranuide in trifluoroacetic acid: New, efficient, general preparation of alkylferrocenes
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Alkylferrocenes are obtained in excellent yields by ionic hydrogenation of ferrocenyl aldehydes and ketones using sodium boranuide and trifluoroacetic acid.
- Bhattacharyya, Sukanta
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- Ionic hydrogenation of acylferrocenes using zinc borohydride: An efficient, mild method for the preparation of alkylferrocenes
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An effective mild procedure for the reductive deoxygenation of α-ferrocenyl aldehydes, ketones, and alcohols into the corresponding alkylferrocenes is described using a combination of zinc borohydride and zinc chloride. This is the first example of such reactivity of zinc borohydride. The present method allows the synthesis of alkylferrocenes bearing terminally functionalized pendant chains.
- Bhattacharyya, Sukanta
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- Redox-active binary eutectics: Preparation and their electrochemical properties
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Eutectics are emerging as promising candidate for electrochemical energy storage. However, the eutectics usually show high viscosity that usually arises from strong intermolecular interactions greatly limits their application. In this communication, we design and prepare two redox-active molecules that both are able to form binary eutectics with TBMA-TFSI. Combined experimental and computational studies indicate the intermolecular interaction is weakened after eutectic formation, resulting in decreased viscosity and enhanced ionization ratio of TBMA-TFSI without affecting the redox behaviors of the individual molecules. Further, the redox-active binary eutectic is used as solvent-free electrolyte for battery application.
- Chen, Hui,Niu, Zhihui,Zhao, Yu
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- Preparation method of diethylferroene with purity being greater than 99%
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The invention relates to a preparation method of diethylferroene with purity being greater than 99%. The preparation method comprises the steps that high-content diacetylferrocene crude products are synthesized through an acylation technology firstly; a recrystallization and column separation series-connection method is utilized to separate the synthesized crude products, and thus high-content diacetylferrocene intermediates are obtained; and then the intermediates are reduced through a reduction catalyst and separated and purified, and thus the high-purity diethylferroene is obtained. The preparation method has the beneficial effects that 1, the purity of the intermediate diacetylferrocene with the large polarity difference is increased to be greater than 99% through a chromatographic column purification method, and the fact is the key for obtaining the high-purity target product; and 2, a high-purity borane-methyl sulfide complex with the extremely-high catalytic efficiency is selected, compared with an amalgam reduction method, the synthesis condition is mild, post-treatment is easy, and environmental protection is achieved.
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Paragraph 0037; 0038; 0039
(2019/12/25)
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- Ferrocenyl-based redox-reversible surfactant and preparation method of thereof
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The invention provides a ferrocenyl-based redox-reversible surfactant and a preparation method thereof, and relates to the field of redox switch type surfactants. The ferrocenyl-based redox-reversible surfactant is prepared from a precursor compound ferrocene, acetyl chloride, zinc amalgam, bromoundecanoic acid, thionyl chloride and trimethylamine as raw materials. The synthesized surfactant molecules are easy to prepare, the yield of the intermediate diacetylferrocene is effectively improved, a new feeding sequence is provided, and the problem of reduction of ferrocene due to oxidation reaction is effectively solved. The surfactant can be used as an electrode surface modification material for glucose detection.
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Paragraph 0020; 0022
(2018/01/19)
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- One-pot synthesis of 1,1′-bis(2-amino)ethyl-substituted ferrocenes from the reaction of spiro[2.4]hepta-4,6-diene with lithium amides: An expedient route into functionalized ferrocenophanes
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The reaction of lithium amides with spiro[2.4]hepta-4,6-diene 2 affords the corresponding (2-aminoethyl)CpLi cyclopropane-ring-opened product that can be trapped in situ with FeCl2 to provide a direct route into 1,1′-bis-aminoethyl ferrocenes 3. In addition to the desired bis-amine products, a number of interesting ferrocene byproducts have been identified. Their formation can be attributed to the associated Bronsted basicity of the lithium amide nucleophiles and their ability to participate in SET processes, opening-up alternative reaction pathways. The desired aminoethyl-substituted ferrocene products are derived primarily from direct nucleophilic cyclopropane ring-opening rather than via amidolithiation of vinylCp intermediates.
- Joly, Kevin M.,Kariuki, Benson M.,Coe, Diane M.,Cox, Liam R.
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p. 358 - 366
(2008/10/09)
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- Highly efficient reduction of ferrocenyl derivatives by borane
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Borane, as a DMS or a THF complex, can efficiently reduce a large range of ferrocenyl derivatives (aldehydes, ketones, ethers, acetals, carboxylic acids, esters,...) if they bear at least one oxygen at a carbon at the α position. On the contrary, similar molecules, which contain nitrogen instead of oxygen, do not react with borane.
- Routaboul, Lucie,Chiffre, Jér?me,Balavoine, Gilbert G.A.,Daran, Jean-Claude,Manoury, Eric
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p. 364 - 371
(2007/10/03)
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- Efficient regio- and diastereo-controlled synthesis of 1,1′- and 1,1′,2,2′-functionalised ferrocenes and the formation of 2-oxa[3]ferrocenophanes
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The synthesis of a C2 symmetric 1,1′ ,2,2′-tetrasubstituted ferrocene system was discussed. The route involved the reduction of ferrocenyl carbonyl compounds which gave access to a range of alcohols, alkenes, alkanes, ethers, and 2-oxa[3]ferrocenophanes depending on the precise conditions used. The loss of optical activity of 1,1′-bis(hydroxymethyl)ferrocenes and 1,1′-bis(hydroxymethyl)ruthenocenes, which had been prepared by asymmetric reduction, was demonstrated in an acidic medium by extensive 1H NMR studies.
- Carroll, Michael A.,White, Andrew J.P.,Widdowson, David A.,Williams, David J.
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p. 1551 - 1557
(2008/10/08)
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- An expedient, mild, reductive method for the preparation of alkylferrocenes
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Reductive deoxygenation of acylferrocenes to the corresponding alkylferrocenes proceeded in excellent yields on utilizing a combination of sodium cyanotrihydroborate and boron trifluoride-diethyl ether.This method allows the synthesis of alkylferrocenes with functionalized tethers and is adaptable to large-scale preparations.
- Bhattacharyya, Sukanta
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p. 4617 - 4620
(2007/10/03)
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- Trimethylchlorosilane-modified Clemmensen reduction of metallocenyl ketones: Trapping and X-ray structures of aliphatic, olefinic, silylated pinacolic, and rearranged pinacolonic products
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The Clemmensen reduction of a carbonyl group to give, in the simplest cases, a methylene unit, is one of the more familiar reactions in organic chemistry. Trimethylchlorosilane as a replacement for the proton allows controlled reductive deoxygenation of carbonyl compounds under formally anhydrous conditions as an alternative to the McMurry dicarbonyl coupling reaction. Aromatic carbonyl compounds with electron-donor substituents are preferred substrates for this reaction to yield symmetrical olefins in good yield. The high donor capacity of metallocenyl groups should especially favor the clean formation of olefins from the corresponding metallocenyl ketones. In this study, a number of ferrocenyl and ruthenocenyl aldehydes and ketones were treated with Zn and trimethylchlorosilane under controlled anhydrous reaction conditions with (a) catalytical and (b) low amounts of H+ present. The observed main products include alkanes, alkenes, silylated pinacols, and rearranged pinacolones, which have been characterized by spectroscopic methods and by X-ray analyses. The diverse outcome in these reactions indicates a reaction mechanism which involves electrophilic catalysis with different energetically similar pathways.
- Denifl, Peter,Hradsky, Andreas,Bildstein, Benno,Wurst, Klaus
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- On the Electron-Proton-Electron Mechanism for 1-Benzyl-1,4-dihydronicotinamide Oxidations
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The reaction of 1-benzyl-1,4-dihydronicotinamide (BNAH) with serveral ferrocenium (Fc+) salts in aqueous propanol was studied.The mechanism was shown to involve electron-proton-electron transfer with rate-limiting electron transfer from BNAH to Fc+.From the rate constants and E0(BNAH/BNAH.+) was estimated to be 0.89 V (SCE).The electrochemistry of BNAH was investigated in order to evaluate a previously determined E0(BNAH/BNAH.+).A reconsideration of the literature data for (non-DDQ) quinone oxidations of reduced nicotinamide adenine dinucleotide (NADH) in water and BNAH in CH3CN shows that the data are consistent with a hydride-transfer mechanism and inconsistent with an electron-proton-electron mechanism involving free NADH.+.A mechanismin which the hydride is transferred by electron-proton-electron transfer within one complex cannot be excluded.
- Miller, Larry L.,Valentine, James R.
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p. 3982 - 3989
(2007/10/02)
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- Chemistry via metal atom cocondensation: Isomerization and complexation reactions of organocyclopropanes and spirocycles
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Reactions of metal atoms with structurally diverse organocyclopropanes have been studied. Quadricyclane (4) is isomerized to norbornadiene (5) upon cocondensation with a variety of metals, but control experiments suggest this reaction is heterogeneously catalyzed by metal aggregates which form upon warming the matrix. Norcarane (6), 2-norcarene (7), 3-carene (8), and 3-norcarene (9) give no reaction when cocondensed with a broad spectrum of metal atoms, despite the presence of an olefinic group in the latter three. When cyclopropylbenzene (11) is cocondensed with chromium, only bis(cyclopropylbenzene)chromium(0) (12) is formed. However, reaction of iron atoms with spiro[2.4]hepta-4,6-diene (14) yields a 14:64:6:17 ratio of 1,1′-diethylferrocene (15), 1-ethyl-1′-vinylferrocene (16), 1,1′-divinylferrocene (17), and [4]ferrocenophane (18) in 44% yield based upon iron. Cocondensations of iron with spiro[2.4]heptane (20; no reaction) and spiro[4.4]nona-1,3-diene (23; formation of bis(tetrahydroindenyl)iron (24) and 1,2-tetramethylene-1′-butylferrocene (25)) are also reported. Possible mechanisms of spirocycle (14, 23) ring opening and product formation are discussed. No volatile bis(arene)chromium(0) complexes are formed when benzocyclopropene (27) and dispiro[2.2.2.2]deca-4,9-diene (28) are cocondensed with chromium, although the former is polymerized. The preparation of 18 from 1,1′-dilithioferrocene (19) and 1,4-dibromobutane is also described.
- Lee Hanlan,Ugolick,Fulcher,Togashi,Bocarsly,Gladysz
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p. 1543 - 1551
(2008/10/08)
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