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A base-free nickel-catalyzed hydroboration of unreactive simple alkenes with bis(pinacolato)diboron using methanol as the hydride source under mild conditions has been developed. Methanol as the solvent proved to be critical for the base-free conditions and high reactivity. A series of linear alkylboronates were synthesized in moderate to excellent yields with high regioselectivity.

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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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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.

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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 forces between colloidal probes and several polymer films were measured by atomic force microscopy in the presence of a series of electrolyte solutions. For Nafion films using a negatively charged silica tip, a repulsive force was obtained at different concentrations of NaClO4. A similar result was obtained for an anion exchange membrane with a positively charged probe. Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was employed to calculate the surface potential and hence, the surface charge. The surface charge density (a¿¼0.3I¼C/cm2) was independent of electrolyte concentration. The slope for plot of potential drop vs In[cs] was a¿¼0.020 V. A theoretical treatment based on GCS theory was employed to account for the above results. For a poly(vinylferrocene) (PVF) film, potential-dependent force curves were obtained, which were qualitatively different from that previously reported for an electronically conducting polymer film electrode.

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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 hexachloroplatinic acid-catalysed hydrosilylation of vinylferrocene by octahydrosilasesquioxane H8Si8O12 to the first organometallic monosubstituted octasilasesquioxane <(eta-C5H5)Fe(eta-C5H4CH2CH2)>– H7Si8O12 has been achieved.

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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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Difluoroethylsulfonium salt, Ph2S+CH2CF2H OTf?, was developed into a convenient difluoromethylcarbene reagent for the iron-catalyzed cyclopropanation of terminal olefins, giving various difluoromethyl-cyclopropanes with excellent diastereoselectivities and in high yields.

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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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Hydrosilylation of vinyl ferrocene with allylhydridopolycarbosilane was used to synthesize a processable hyperbranched polyferrocenylcarbosilane (HBPFCS), which was characterized by combination of gel permeation chromatography, Fourier transform infrared (FT-IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. The polymer-to-ceramic transformation of the HBPFCSs was then investigated by FT-IR and 13C MAS NMR spectroscopy as well as by thermal gravimetric analysis (TGA). A self-catalytic effect of ferrocenyl units in the HBPFCS skeleton on dehydrocoupling was found during a curing process at 170C resulting in a high ceramic yield of ca. 80% at 1200C in Ar. Finally, microstructures and magnetic properties of the final ceramics were studied by techniques such as X-ray diffraction, energy dispersive spectroscopy, Raman spectroscopy, transmission electron microscopy and vibrating sample magnetometry. The final ceramic (pyrolysis temperature ?900 C) is characterized by a microstructure comprised of a SiC/C/Fe nanocomposite. Turbostratic carbon layers located at the segregated alpha-Fe crystal boundary avoid interdiffusion and explain the exclusive existence of alpha-Fe in a SiC/C matrix even at 1300 C. Variations of the iron content in the HBPFCSs and of the pyrolysis conditions facilitate the control of the composition and ceramic micro/nanostructure, influencing in particular magnetic properties of the final SiC/C/Fe nanocomposite ceramic.

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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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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.

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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 present application provides processes and intermediates useful in the production of beta- aminocarbonyl- or beta-aminothiocarbonyl-containing compounds. Provided herein is a process for synthesizing beta-aminocarbonyl- or beta-aminothiocarbonyl-containing compounds from an alkene and a hydrazone. Also provided herein is a process for synthesizing beta-aminocarbonyl- or beta-aminothiocarbonyl-containing compounds from an alkene and a hydrazine. The present application further provides intermediate aminoisocyanate and iminoisocyanate compounds, and methods for synthesizing the starting hydrazone and hydrazine 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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The wide dissemination of catalytic protocols in academic and industrial laboratories is facilitated by the development of catalysts that are not only highly active but also user-friendly, stable to moisture, air and long term storage and easy to prepare on a large scale. Herein we describe a protocol for the Heck-Mizoroki reaction mediated by cyclopalladN-dimethylbenzylamine (dmba) ligated ne, 1,3-bdot;HCl in refluxing acetonitrile in air in the presence of K2CO in iates the H bromides in reagent grade NMP at the 0.1-2 mol% range without the need for rigorous anhydrous techniques or a glovebox, and is active even in air. The catalyst is capable of achieving very high levels of catalytic activity (TON of up to 5.22 × 105) for the coupling of a deactivated arylbromide, p-bromoanisole, with tBu acrylate as a benchmark substrate pair. A wide range of aryl bromides, iodides and, for the first time with a NHC-Pd catalyst, a triflate was coupled with diverse acrylate derivatives (nitrile, tert-butyl ester and amides) and styrene derivatives. The use of excess (>2 equiv.) of the aryl bromide and tert-butyl acrylate leads to mixture of tert-butyl beta,beta-diarylacrylate and tert-butyl cinnamate derivatives depending on the substitution pattern of the aryl bromide. Electron rich m- and p-substituted arylbromides give the diarylated products exclusively, whereas electron-poor aryl bromides give predominantly mono-arylated products. For o-substituted aryl bromides, no doubly arylated products could be obtained under any conditions. Overall, the active catalyst (IMes-Pd) shows higher activity with electron-rich aryl halides, a marked difference compared with the more commonly used phosphane-Pd or non-ligated Pd catalysts.

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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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New ferrocenyl-based star-shaped complexes have been obtained by palladium-catalyzed reactions. The synthetic method reported shows an advantage over the traditional Wittig reaction for the synthesis of olefinated compounds, both in yields and in selectivity towards the all-E isomers. The electrochemistry of the compounds has been studied. The crystal structure of E-ferrocenyl-4-(vinylphenyl)vinylene, one of the starting complexes to the star-shaped compounds, has been determined by means of single crystal X-ray diffraction.

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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