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The enantioselective, intermolecular hydroallylation of vinylarenes employing allylic phosphate electrophiles has been achieved through a copper hydride catalyzed process. The protocol described herein can be applied to a diverse set of vinylarene substrates and allows for the installation of the parent allyl group as well as a range of 2-substituted allylic fragments.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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The metallocene cation complex [Cp*2ZrCH3] +[B(C6F5)4]- inserts the phosphino-substituted alkyne Ph-Ci – 1/4C-PPh2 into the [Zr]-CH3 bond to form the internally phosphane-stabilized cation [Cp*2Zr-C(=CMePh)PPh2]+ (10). Complex 10 adds alkyl isocyanides as well as pivalonitrile at a lateral site at the bent metallocene wedge with retention of the Zr-P bond. Complex 10 acts as a reactive frustrated Lewis pair toward heterocumulenes, undergoing Zr+/P addition reactions to the carbonyl groups of an alkyl isocyanate and of carbon dioxide to form the respective five-membered metallaheterocyclic adducts 13 and 14. With mesityl azide complex 10 undergoes a Zr+/P FLP N,N-addition reaction at the terminal azide nitrogen atom to form the four-membered FLP cycloadduct 15. The Zr+/P FLP is a reactive hydrogen activator. In a stoichiometric reaction it generates a hydridozirconocene cation that subsequently serves as a hydrogenation catalyst for various olefinic or acetylenic substrates. The Zr+/P pair 10 undergoes selective 1,4-addition reactions to conjugated enones and to a conjugated ynone to give the corresponding seven-membered metallacyclic Zr+/P FLP addition products. Many compounds of this study were characterized by X-ray diffraction.

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This paper describes the orbital configuration which provides a basis for the understanding of the electronic structure and spectroscopic properties of 17e and 18e FcC2R and FcC4R dyads, where R is H, 1-naphthyl, 9-anthryl, 3-pyrenyl, perylenyl. DFT calculations show that destabilisation of the ferrocenyl pi orbitals upon binding a C{triple bond, long}CR group to a Cp ring leads to the metal-based a1 orbital dropping below the e1-a so that the frontier orbital configuration is (e2? -a, pi)2 (e2? -b,metal)2 (e1? -a, pi)2, (a1, metal)2. The contribution of the aryl group to the pi e2-a and e1-a orbitals varies with the annelation of the ring. The LUMO is aryl based. The calculations are consistent with the spectroscopic data for the 18e species. Oxidation to the 17e cations does not change the orbital configuration but the orbital energies are lowered by the positive charge centred on the Fe. A strongly solvatochromic transition in the near-IR, a signature for the 17e cations, is best described as an LMCT transition but the contribution of C2R and C4R to the donor and acceptor levels depends on the ionization energy of the aryl pi orbital. LMCT energies decrease from FcC2R to FcC4R dyads.

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Pd(OAc)2-catalyzed Sonogashira coupling reactions of alkynes and a variety of aryl halides with 1,3-bis(5-ferrocenylisoxazoline-3-yl)benzene as an efficient non-phosphorus ligand under copper-free conditions are presented. The main advantages over previous methodologies include low catalyst loading (0.2 mol% Pd(OAc)2 and 0.4 mol% ferrocenyl bisoxazoline ligand are sufficient for these coupling reactions), less problematic reaction medium (water?dimethylformamide) and more convenient operation (no requirement for nitrogen protection).

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3,5-Disubstituted isoxazolines and isoxazoles have been synthesized using 1,3-dipolar cycloaddition of ferrocene derivatives FcCH=CH2, FcCOCH=CH2 and FcC<*>CH with aliphatic and aromatic carbonitrile N-oxides. – Key words: vinylferrocene, acryloylferrocene, ethynylferrocene; 1,3-dipolar cycloaddition reactions with aliphatic and aromatic carbonitrile oxides.

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Herein, we report a fast, mild, efficient and simple Wittig reaction in a dry state to get ferrocenylethene derivatives. The Z and E isomers can be separated by chromatography and many isomers are characterized for the first time.

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A series of ferrocenyl mono- and polynuclear complexes conjugated to imino and amino scaffolds was prepared. The imino complexes were prepared via a Schiff base condensation reaction between (E)-4-vinylferrocenylbenzaldehyde and various amines. The amino complexes were prepared by reductive amination reactions using the same precursors. The compounds were characterized using standard spectroscopic and analytical techniques including Nuclear Magnetic Resonance (NMR) spectroscopy, Infrared (IR) spectroscopy and mass spectrometry. The compounds were screened against Mycobacterium tuberculosis as well as the NF54 chloroquine-sensitive (CQS) strain of Plasmodium falciparum. Overall, the complexes showed moderate in vitro biological activity, with the ferrocenylimines exhibiting enhanced activity against M. tuberculosis compared to the corresponding amines. The ferrocenylimines also displayed moderate activity against P. falciparum, with the second-generation polyimine complex exhibiting the highest activity in vitro. The ferrocenylamines exhibit promising antiplasmodial activity, enhanced compared to the imines, with the silicon-containing derivative and the second-generation dendrimer showing good activity.

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Upon photoirradiation, diphenyl diselenide and diphenyl ditelluride reacted with ethynylferrocene to afford the corresponding bischalcogenated vinylferrocenes. Regioand stereoselectivities were determined by X-ray crystal analysis, and redox properties were investigated by cyclic voltammetry.

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Ferrocenylmethylation and alpha-ferrocenylethylation of indazole were carried out for the first time. Both reactions afforded two isomers, which were characterized by physical and physicochemical methods, among them by X-ray diffraction analysis. 1-(alpha-Ferrocenylethyl)indazole is thermally more stable than the 2-substituted isomer. Both isomers serve as ferrocenylalkylating agents with respect to s-triazole.

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In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. SDS of cas: 1271-51-8. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1271-51-8, Name is Vinylferrocene

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