Contemporary Developments in Ferrocene Chemistry: Physical, Chemical, Biological and Industrial Aspects

Molecules, Journal Year: 2023, Volume and Issue: 28(15), P. 5765 - 5765

Published: July 30, 2023

Ferrocenyl-based compounds have many applications in diverse scientific disciplines, including polymer chemistry as redox dynamic polymers and dendrimers, materials science bioreceptors, pharmacology, biochemistry, electrochemistry, nonlinear optics. Considering the horizon of ferrocene chemistry, we attempted to condense neoteric advancements synthesis derivatives reported literature from 2016 date. This paper presents data on progression classes organic having scaffolds recent developments ferrocene-based organometallic compounds, with a special focus their biological, medicinal, bio-sensing, chemosensing, asymmetric catalysis, material, industrial applications.

Language: Английский

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Nanoparticles as Heterogeneous Catalysts for ppm Pd-Catalyzed Aminations in Water

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(5), P. 1997 - 2008

Published: Jan. 22, 2024

A general protocol employing heterogeneous catalysis has been developed that enables ppm of Pd-catalyzed C-N cross-coupling reactions under aqueous micellar catalysis. new nanoparticle catalyst containing specifically ligated Pd, in combination with nanoreactors composed the designer surfactant Savie, a biodegradable amphiphile, catalyzes bond formations recyclable water. variety coupling partners, ranging from highly functionalized pharmaceutically relevant APIs to educts Merck Informer Library, readily participate these environmentally responsible, sustainable reaction conditions. Other key features associated this report include low levels residual Pd found products, recyclability medium, use ocean water as an alternative source options for pseudohalides and

Language: Английский

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Simplified Preparation of ppm Pd-Containing Nanoparticles as Catalysts for Chemistry in Water

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(5), P. 3179 - 3186

Published: Feb. 17, 2023

A protocol has been developed that not only simplifies the preparation of nanoparticles (NPs) containing ppm levels ligated palladium affect heterogeneous catalysis but also ensures they afford products cross-couplings reproducibly due to freshly prepared nature each reagent. Four different types couplings are studied: Suzuki-Miyaura, Sonogashira, Mizoroki-Heck, and Negishi reactions, all performed under mild aqueous micellar conditions. The simplified process relies on initial formation stable, storable Pd- ligand-free NPs, which is then added appropriate amount Pd(OAc)2 ligand-matched desired type coupling, in water.

Language: Английский

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It Is Not All about the Ligands: Exploring the Hidden Potentials of tBu₃P through Its Oxidative Addition Complex as the Precatalyst

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(12), P. 8106 - 8118

Published: June 1, 2023

A series of oxidative addition complexes with a general formula (tBu3P)Pd(Ar)X, as class precatalysts, were synthesized for challenging Suzuki–Miyaura coupling involving partners, such (i) sensitive polyfluorinated arylboronic acids or their corresponding boronic esters, (ii) sterically hindered electrophiles, and (iii) nucleophiles. total 89 examples are reported, which 39 in the Supporting Information. These particular (tBu3P)Pd(4-CF3Ph)Br, demonstrated to be powerful catalytic systems cross reactions comparison situ created by mixing tBu3P ligand palladium precursor. The precatalysts also superior other monoligated systems, Buchwald's biaryl based G3 G4 palladacycles. In addition, (tBu3P)Pd(4-CF3Ph)Br precatalyst is highly effective second most popular reaction, namely Buchwald–Hartwig coupling. this study, electron-deficient amines coupled (hetero)aryl bromides chlorides 34 examples, 8 Interestingly, results obtained both C–C C–N couplings on par that "state-of-the-art" catalysts containing Ad3P Np3P ligands same similar substrates, suggesting it not all about ligands.

Language: Английский

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ppm Pd‐Containing Nanoparticles as Catalysts for Negishi Couplings … in Water

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(39)

Published: Aug. 3, 2022

Abstract New technology is reported that enables Negishi couplings to be run under sustainable, far greener conditions. Thus, ppm Pd‐containing nanoparticles (NPs) have been developed catalyze in recyclable water very mild These heterogeneous reactions involve loadings of Pd typically only 2500 (0.25 mol %). Highly functionalized aromatic and heteroaromatic bromides readily participate, including examples taken from the Merck Informer Library indicative functional group tolerance associated with these couplings. Direct comparisons existing literature routes are made. Very low residual levels newly formed products expected, as determined by ICP‐MS. The reagent involved has extensively characterized via DLS, TEM, cryo‐TEM, EDX measurements.

Language: Английский

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Isolation and Characterization of Heteroleptic Mononuclear Palladium(I) Complexes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(43), P. 20008 - 20015

Published: Oct. 18, 2022

Catalytic transformations involving Pd(0)/Pd(II) catalytic cycles are very well known, and processes high-valent Pd(III) Pd(IV) low-valent Pd(I) intermediates have also gained interest in recent years. Although proposed these cycles, isolated characterized mononuclear species rare. Herein, we report the isolation of two heteroleptic complexes stabilized by dithiapyridinophane ligands that were fully single-crystal X-ray diffraction; EPR, IR, UV–vis spectroscopies; computational studies. Excitingly, one shows Kumada Csp3–Csp2 cross-coupling competency, initial studies other direct evidence for Csp3–H bond activation to occur at center.

Language: Английский

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Recent Advances in Transition‐Metal‐Catalyzed C−H Functionalization of Ferrocene Amides

Chemistry - An Asian Journal, Journal Year: 2022, Volume and Issue: 17(21)

Published: Sept. 1, 2022

Abstract During the past decades, in synthetic organic chemistry, directing‐group‐assisted C−H functionalization is found to be a key tool for expedient and site‐selective construction of C−C hybrid bonds. Among ferrocene derivatives, directed group strategy undoubtedly most commonly used method. Compared other directing groups, amides can synthesized easily are now recognized as one efficient tools selective certain positions because its metal centre permits fine, tuneable reversible coordination. The family amide groups mainly comprises monodentate bidentate which categorized on basis coordination sites. In this review, various bond reactions using broadly discussed.

Language: Английский

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Purple Light-Promoted Coupling of Bromopyridines with Grignard Reagents via SET

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 7148 - 7155

Published: May 8, 2024

Alkyl- and arylpyridines 2,2′-bipyridines are conventionally prepared by Minisci reactions of pyridines transition metal-catalyzed coupling halopyridines. Herein, purple light-promoted radical 2- or 4-bromopyridines with Grignard reagents in Et2O a mixture tetrahydrofuran regular glassware without the need for metal catalyst were disclosed first time. Methyl, primary secondary alkyl, cycloalkyl, aryl, heteroaryl, pyridyl, alkynyl compatible protocol. As result, alkyl- easily prepared. Single electron transfer from reagent to bromopyridine was stimulated light. An extruded dimerization worked as catalyst. Light on/off experiments indicated that constant irradiation required product formation. Studies clock substrates verified involvement pyridyl noninvolvement an alkyl aryl reagent. The available proof supports photoinduced SRN mechanism new reactions.

Language: Английский

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Formation of exceptional monomeric YPhos–PdCl₂complexes with high activities in coupling reactions

Chemical Science, Journal Year: 2022, Volume and Issue: 13(45), P. 13552 - 13562

Published: Jan. 1, 2022

The use of well-defined palladium(ii) complexes as precatalysts for C-X cross-coupling reactions has improved the palladium catalysts in organic synthesis including large-scale processes. Whereas sophisticated Pd(ii) precursors have been developed past years to facilitate catalyst activation well handling systems with more advanced monophosphine ligands, we herein report that simple PdCl2 function efficient ylide-substituted phosphines (YPhos). These are readily synthesized from sources and form unprecedented monomeric without need any additional coligand. Instead, these structures stabilized through a unique bonding motif, which YPhos ligands bind metal adjacent phosphine ylidic carbon site. DFT calculations showed bonds both dative interactions stronger interaction originating electron-rich donor. This mode leads remarkable stability even towards air moisture. Nonetheless, monoligated LPd(0) thus active palladium(0) species coupling reactions. Accordingly, YPhos-PdCl2 serve highly series C-C Despite their simplicity they can compete efficiency complex less stable precatalysts.

Language: Английский

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Synthesis, coordination behavior, and catalytic properties of dppf congeners with an inserted carbonyl moiety

New Journal of Chemistry, Journal Year: 2022, Volume and Issue: 46(45), P. 21536 - 21552

Published: Jan. 1, 2022

Dppf-type ligands, desymmetrized by an inserted carbonyl group coordinate Pd( ii ) and Pd(0). Among the air-stable Pd(0) complexes, compound containing least electron-donating ligand gives best catalytic results in Stille reaction.

Language: Английский

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