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PROCESS FOR THE SYNTHESIS OF BETA-AMINOCARBONYLS

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.

PROCESS FOR THE SYNTHESIS OF BETA-AMINOCARBONYLS

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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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A novel synthesis, characterization and biological studies of ferrocenyl substituted pyrazoles

It has been discovered that ferrocenyl substituted heterocyclic compounds have wide scope of restorative methodology. The combination of ferrocenyl substituted pyrazole is the new class in these compounds with upgraded natural activity. This work center around blend of ferrocenyl substituted pyrazoles through novel course. The combination of 1-phenyl-3-ferrocenyl-pyrazole was examined including addition-cyclocondensation like response conditions. The response continued through three phases using of expansion cyclo-buildup of acetyl ferrocene with phenyl hydrazine pursued by cyclizing reagent iodine with NaHCO3. In both syntheses, each time single product isolated having good yields (87 and 79 %). Ferrocenyl substituted pyrazoles were examined by spectroscopic techniques (1H NMR, IR, MS) and their biological properties have been screened.

A novel synthesis, characterization and biological studies of ferrocenyl substituted pyrazoles

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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 regio- and diastereo-controlled synthesis of 1,1?- and 1,1?,2,2?-functionalised ferrocenes and the formation of 2-oxa[3]ferrocenophanes

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.

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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Reference£º
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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Mono- and multimeric ferrocene congeners of quinoline-based polyamines as potential antiparasitics

A series of mono- and multimeric polyamine-containing ferrocenyl complexes containing a quinoline motif were prepared. The complexes were characterised by standard techniques. The molecular structure of the monomeric salicylaldimine derivative was elucidated using single crystal X-ray diffraction and was consistent with the proposed structure. The antiplasmodial activity of the compounds were evaluated in vitro against both the NF54 (chloroquine-sensitive) and K1 (chloroquine-resistant) strains of Plasmodium falciparum. The polyamine derivatives exhibit good resistance index values suggesting that these systems are beneficial in overcoming the resistance experienced by chloroquine. Mechanistic studies suggest that haemozoin formation may be the target of these quinoline complexes in the parasite. Some of the complexes exhibit moderate to high cytotoxicity against WHCO1 oesophageal cancer cells in vitro. The monomeric ferrocenyl-amine complexes exhibit potent activity against this particular cell line. The complexes were also screened against the G3 strain of Trichomonas vaginalis and the salicylaldimine complexes demonstrated promising activity at the tested concentration. All of these compounds show no inhibitory effect on several common normal flora bacteria, indicative of their selectivity for eukaryotic pathogens and cancer.

Mono- and multimeric ferrocene congeners of quinoline-based polyamines as potential antiparasitics

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Reference£º
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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Substitution effects at bridging vinyl ligands: molecular structures of where R = OEt or ferrocenyl

The two related compounds (R = OEt or ferrocenyl C5H4FeC5H5, Fc), have been prepared, the first by insertion of ethyl ethynyl ether (CH<*>COEt) into and the second by oxidative addition of ethenylferrocene (CH2 = CHFc) to respectively.Spectroscopically both compounds are similar to known related compounds with alkyl- or aryl-substituted vinyl ligands.A single-crystal X-ray structural study of each was made in an attempt to detect any structural effects of ?-donation by the substituents at the vinylgroup, such as was observed for .The latter compound has been shown to have a zwitterionic structure with an alkylidene bridge between two osmium atoms rather than the normal mu,eta2-vinyl mode of bonding.The two compounds studied here have essentially normal mu,eta2-vinyl bridges, but with some distortion towards the alkylidene bonding type, more pronounced for R = OEt.

Substitution effects at bridging vinyl ligands: molecular structures of where R = OEt or ferrocenyl

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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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Design, synthesis and characterization of ferrocene based V-shaped chromophores with modified nonlinear effect

In order to prepare D-pi-A-pi-D analogs have the ability to use in optical applications, 4H-pyran fragment conjugated with two styryl groups and their combination play pi-spacer role between donor and acceptor groups. Malononitrile and 1, 3-indandione play as acceptor groups and ferrocene nuclei was chosen as donor group. 1H and 13C NMR, FT-IR and mass spectroscopy and CHN analysis were used to confirm the structure of synthesized compounds. Electrochemical, photochemical and photophysical properties of these compounds were studied. The third order nonlinear refractive index, n2, and nonlinear absorption coefficient, beta, of synthesized chromophores were assessed by the open and closed aperture Z-scan measurements, respectively. The quantum chemistry study was performed on synthesized compounds with the DFT approach. The theoretical and experimental results show that these compounds can be considered as candidates to be used in optical applications.

Design, synthesis and characterization of ferrocene based V-shaped chromophores with modified nonlinear effect

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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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Novel isoxazoline ligand with ferrocene backbone: Preparation and application in Heck reaction with water as solvent

Two novel isoxazoline N,N-bidentate ligands with ferrocene backbone have been synthesized and employed for the palladium-catalyzed Heck coupling reaction. Among them, 1,3-bis-(5-ferrocenylisoxazoline-3-yl)benzene was found to be thermally stable and a highly effective ligand for Heck coupling reaction in neat water without N2 protection, affording the desired coupling products in good to excellent yield with high diastereoselectivity. The developed catalytic system was also well workable for 1,2-disubstituted alkenes, which were less involved in the Heck reaction for its larger steric hindrance. Copyright

Novel isoxazoline ligand with ferrocene backbone: Preparation and application in Heck reaction with water as solvent

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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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Rhodium- and ruthenium-catalyzed dehydrogenative borylation of vinylarenes with pinacolborane: Stereoselective synthesis of vinylboronates

The treatment of pinacolborane (4,4,5,5-tetramethyl-1,3,2- dioxaborolane) with vinylarenes in the presence of a catalytic amount of phosphine-free di-mu-chlorobis(1,5- cyclooctadiene)dirhodium(I) [RhCl(cod)]2, through dehydrogenative borylation, provides the corresponding regio- and stereodefined (E)-2-arylethenylboronates in high yields. Also, a ruthenium complex prepared in situ from (1,5-cyclooctadiene)(1,3,5-cyclooctatriene)ruthenium(O) [Ru(cod)(cot)] and P(4CF3C6H4)3 showed considerable catalytic activity for dehydrogenative borylation.

Rhodium- and ruthenium-catalyzed dehydrogenative borylation of vinylarenes with pinacolborane: Stereoselective synthesis of vinylboronates

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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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Cycloaddition of o-Carboryne with Vinyl Ethers: Synthesis of Carborane-Fused Cyclobutanes

o-Carboryne (1,2-dehydro-o-carborane) is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Using 1-Li-2-OTf-o-C2B10H10 as a precursor, o-carboryne undergoes an efficient [2 + 2] cycloaddition with a large variety of vinyl ethers at room temperature to give a series of carborane-fused cyclobutanes in very good to high isolated yields. This reaction is compatible with many functional groups and has a very broad substrate scope ranging from alkyl- to aryl- and to silyl-substituted vinyl ethers. A stepwise reaction mechanism is proposed based on the control experiments, which is supported by DFT calculations. All new compounds have been fully characterized by 1H, 13C, and 11B NMR spectroscopy as well as HRMS spectrometry. Some are further confirmed by single-crystal X-ray analyses.

Cycloaddition of o-Carboryne with Vinyl Ethers: Synthesis of Carborane-Fused Cyclobutanes

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Reference£º
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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A versatile electrochemical sensing receptor based on a molecularly imprinted polymer

Electrochemical molecularly imprinted polymers (e-MIPs) are reported for the first time. Their elaboration is based on the introduction of a redox tracer (vinylferrocene) inside the binding cavities of a cross-linked MIP. Determination of the analyte (benzo[a]pyrene) can be simply performed by measuring the redox tracer signal. the Partner Organisations 2014.

A versatile electrochemical sensing receptor based on a molecularly imprinted polymer

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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