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N-heterocycle carbene (NHC)-ligated cyclopalladated N,N- dimethylbenzylamine: A highly active, practical and versatile catalyst for the Heck-Mizoroki reaction

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 ¡Á 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.

N-heterocycle carbene (NHC)-ligated cyclopalladated N,N- dimethylbenzylamine: A highly active, practical and versatile catalyst for the Heck-Mizoroki reaction

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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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Enantioselective Assembly of Congested Cyclopropanes using Redox-Active Aryldiazoacetates

The enantioselective assembly of quaternary stereocenters through sequential functionalization of versatile carbon-atom precursors has the potential to systematize the synthesis of these ubiquitous stereogenic elements. Herein, we report two catalytic processes that allow the realization of this concept in the enantioselective synthesis of cyclopropanes. We demonstrate that C-H functionalization, carbene-transfer, and decarboxylative cross-coupling can sequentially take place in the same carbon atom to obtain highly enantioenriched cyclopropane products. The reactions reported herein give access to redox-active analogues of privileged aryldiazoacetates and demonstrate their enantioselective carbene transfer with a simple and practical rhodium catalyst.

Enantioselective Assembly of Congested Cyclopropanes using Redox-Active Aryldiazoacetates

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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 METHOXYTHALLATION OF VINYLFERROCENE

Product analysis and kinetic data for the reaction of vinylferrocene with thallium triacetate in methanol are reported.Styrene has also been investigated under similar conditions. 1-Ferrocenyl-1,2-dimethoxyethane was the sole product isolated, since the methoxythallation adduct undergoes solvolysis under the reaction conditions. beta-Methylvinylferrocene yields both addition and substitution products in the reaction with Tl(OAc)3, as well as in the previously described reaction with Hg(OAc)2.

THE METHOXYTHALLATION OF VINYLFERROCENE

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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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Nickel(0)-Catalyzed Hydroalkenylation of Imines with Styrene and Its Derivatives

A nickel(0)-catalyzed hydroalkenylation of imines with styrene and its derivatives is described. A wide range of aromatic and aliphatic imines directly coupled with styrene and its derivatives, thus providing various synthetically useful allylic amines with up to 95 % yield. The reaction offers a new atom- and step-economical approach to allylic amines by using alkenes instead of alkenyl-metallic reagents. Experiments and DFT calculations showed that TsNH2 promotes the proton transfer from the coordinated olefin to the imine, accompanied by a new C?C bond formation.

Nickel(0)-Catalyzed Hydroalkenylation of Imines with Styrene and Its Derivatives

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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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Pd-mediated synthesis of linked conjugated tri- and penta-ferrocenyl complexes

A facile synthesis of new conjugated oligo-ferrocenyl compounds is described. The synthetic method consists of a two step procedure, which combines olefination by the Wittig procedure and Pd-mediated C-C coupling, leading to high yields of tri- and penta-ferrocenyl complexes. The crystal structures of the 1,1?-bissubstituted ferrocenyl precursors are described. The electrochemical analysis of the compounds obtained, reveals that the peripheral ferrocenyl units display an equivalent redox behavior, with a large separation of the peak corresponding to the central ferrocenyl unit.

Pd-mediated synthesis of linked conjugated tri- and penta-ferrocenyl complexes

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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 facile synthesis and ring-opening reactions of novel 2-ferrocenyl-3,4- dihydropyrans

A series of novel 2-ferrocenyl-3,4-dihydropyrans were synthesized in good to excellent yields through three-component reaction of vinylferrocene, 1,3-dicarbonyl compound and formaldehyde near room temperature under catalyst-free conditions. The obtained ferrocenyl dihydropyrans can also react readily with indole in the presence of alum, providing a ring-opening product in high yield, and this result opens an effective way to access a new class of complex ferrocenyl derivatives.

A facile synthesis and ring-opening reactions of novel 2-ferrocenyl-3,4- dihydropyrans

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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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Related Products of 1271-51-8, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.1271-51-8, Name is Vinylferrocene, molecular formula is C12H3Fe. In a article£¬once mentioned of 1271-51-8

Characterization of non-classical C[sbnd]Br?pi interactions in (E)-1,3-dibromo-5-(2-(ferrocenyl)vinyl)benzene and related derivatives of ferrocene

Amongst the halogens, the involvement of bromine atoms in various types of intermolecular interactions is comparatively the least studied. In this manuscript, we report the formation of C[sbnd]Br?pi interactions, with the pi-rings being the cyclopentadienyl (Cp) rings of a ferrocene molecule in a newly synthesized compound (E)-1,3-dibromo-5-(2-(ferrocenyl)vinyl)benzene. We have also performed a detailed quantitative analysis on C[sbnd]Br?pi interactions observed in the synthesized molecule and in several related molecules found in the Cambridge Structure Database (CSD) showing the presence of these interactions. A topological analysis based upon QTAIM theory and electrostatic potential ESP mapped on the Hirshfeld surface of these molecules confirm that these interactions are better described as ?halogen bonds? wherein the electropositive region (sigma-hole) on the Br-atom interacts with the electronegative region over the Cp-ring of the ferrocene. Further, the electronegative region on the bromine atom (perpendicular to the C[sbnd]Br bond) was observed to be involved in the formation of highly directional C[sbnd]H?Br interactions with the ?C[sbnd]Br?H close to 90. Thus the bromine atom is acting as both a ?halogen bond donor? and ?hydrogen bond acceptor? in the crystal packing with the two interactions being mutually orthogonal.

Characterization of non-classical C[sbnd]Br?pi interactions in (E)-1,3-dibromo-5-(2-(ferrocenyl)vinyl)benzene and related derivatives of ferrocene

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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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“Gentle lithography” with benzene on Si(100)

Nanoscale lithography of small- and medium-sized molecules on a clean silicon surface was studied using benzene. A scanning tunneling microscopy (STM)-based nanolithographic method was also investigated. The patterning areas of the surface with ethylene and vinyl ferrocene was also discussed. It was observed that any molecules that remain unsaturated after adsorption are candidates to form a monolayer template for this kind of lithography.

“Gentle lithography” with benzene on Si(100)

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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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Antileishmanial ferrocenylquinoline derivatives: Synthesis and biological evaluation against Leishmania donovani

The emergence of resistance against existing antileishmanial drugs necessitates the search for new classes of antileishmanial compounds. Herein a series of structurally diverse ferrocenylquinolines have been synthesized and evaluated for in?vitro antileishmanial activity against Leishmania donovani using?the MTT assay. Thirteen (M2-M14) substituted ferrocenylquinoline congeners possessing triazole?rings?were generated by palladium mediated Suzuki-Miyaura coupling reaction of 5-iodoferrocenylquinolinetriazole and substituted arylboronic acids. All the synthesized compounds were tested for its antileishmanial activity using both promastigote and amastigote stages of L.?donovani. Among them, three compounds (M4, M7 and M9) exhibited promising anti-promastigote activity, with an IC50value of 28.7?muM, 22.1?muM and 28?muM, respectively, and no cytotoxicity toward host splenocytes. These three compounds are equally effective against the intracellular amastigote stage of L.?donovani showing the IC50values of 16?muM (M4), 8?muM (M7) and 16?muM (M9), respectively, with consistent nitric oxide generation as required for parasite clearance. From the battery of tests conducted in this study, it appears that these compounds induce parasite death by promoting cell cycle arrest and triggering apoptosis.

Antileishmanial ferrocenylquinoline derivatives: Synthesis and biological evaluation against Leishmania donovani

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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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COMPENSATION OF OHMIC VOLTAGE DROP ON MODIFIED POLYMER FILM ELECTRODES

TCNQ and PVF polymer film electrodes have been studied by cyclic voltammetry.It has been established that cyclic voltammetric curves become distorted by uncompensated ohmic resistance for medium thick films at scan rates higher than 0.025 V/s.The effect of ohmic voltage drop can be practically eliminated by the use of an Electroflex GMK (Szeged) potentiostat using the interruption technique.

COMPENSATION OF OHMIC VOLTAGE DROP ON MODIFIED POLYMER FILM ELECTRODES

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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