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The highly enantioselective organocatalytic synthesis of dihydropyran spirocyclic compounds bearing di- and trifluoromethyl groups by aldol cyclization reaction via trienamine using cyclic 2,5-dienones and different di- and trifluoromethylketones is described. Using a bifunctional aminothiourea catalyst, trifluoromethyl-functionalized dihydropyran spirocyclic products were obtained with good yields and enantioselectivities. Subsequent transformation with H2 and Pd/C has allowed the synthesis of the tetrahydropyran structure with three stereocenters. The plausible reaction mechanism was investigated by computational methods.
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Conducting C-C cross-coupling reactions under convenient and mild conditions remains extremely challenging in traditional organic synthesis. In this study, ZnCo2O4@g-C3N4@Cu exhibited extraordinary photocatalytic performance as a new visible light harvesting heterogeneous copper-based photocatalyst in cyanation and Mizoroki-Heck visible-light-driven cross-coupling reactions at room temperature and in air. Surprisingly, by this method, the cyanation and Mizoroki-Heck cross-coupling reactions of various iodo-, bromo- and also the challenging chloroarenes with respectively K4[Fe(CN)6]·3H2O and olefins produced promising results in a sustainable and mild media. The significant photocatalytic performance of ZnCo2O4@g-C3N4@Cu arises from the synergistic optical properties of ZnCo2O4, g-C3N4, and Cu. These components can enhance the charge carrier generation and considerably reduce the recombination rate of photogenerated electron-hole pairs. No need to use heat or additives, applying an economical and benign light source, utilizing an environmentally compatible solvent, facile and low-cost photocatalytic approach, aerial conditions, high stability and convenient recyclability of the photocatalyst are the remarkable highlights of this methodology. Moreover, this platform exhibited the ability to be performed on a large scale, which is considered an important issue in industrial and pharmaceutical use. It is worth noting that this is the first time that a heterogeneous copper-based photocatalyst has been employed in visible light-promoted cyanation reactions of aryl halides.
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The asymmetric catalytic synthesis of 1,2-diamines has received considerable interest, especially in the last ten years, due to their presence in biologically active compounds and their applications for the development of synthetic building blocks, chiral ligands and organocatalysts. Synthetic strategies based on C-N bond-forming reactions involve mainly (a) ring opening of aziridines and azabenzonorbornadienes, (b) hydroamination of allylic amines, (c) hydroamination of enamines and (d) diamination of olefins. In the case of C-C bond-forming reactions are included (a) the aza-Mannich reaction of imino esters, imino nitriles, azlactones, isocyano acetates, and isothiocyanates with imines, (b) the aza-Henry reaction of nitroalkanes with imines, (c) imine-imine coupling reactions, and (d) reductive coupling of enamines with imines, and (e) [3+2] cycloaddition with imines. C-H bond forming reactions include hydrogenation of CîN bonds and C-H amination reactions. Other catalytic methods include desymmetrization reactions of meso-diamines.
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The stereoselective synthesis of vicinal amino alcohols derivatives from 1-substituted cyclopropanols and chiral N-tert-butanesulfinyl imines is described. Cyclopropanols are easily prepared from carboxylic esters upon reaction with ethylmagnesium bromide in the presence of titanium tetraisopropoxide and undergo carbon-carbon bond cleavage by means of diethylzinc to produce, upon base deprotonation, enolized zinc homoenolates, which react with chiral sulfinyl imines in a highly regio- and stereoselective manner.
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Multilayer graphene (MLG), obtained by mild sonication of graphite in NMP, was functionalised via 1,3-dipolar cycloaddition with azomethine ylides generated by thermal 1,2-prototropy from various imino esters. The microwave-assisted functionalisation took place in five hours at 100 °C. The resulting MLG, containing substituted proline-based amine functional groups, was characterized using XPS and showed a nitrogen loading three times that obtained for the same transformation performed for five days using convection-assisted heating. The preparation of the imino ester containing a bipyridine unit at the arylidene position allowed for the preparation of the corresponding functionalised MLG, which incorporated the ruthenium atom to achieve a heterogeneous MLG-Ru complex. This supported complex was tested, as a proof of concept, as a photocatalyst of the aerobic oxidative hydroxylation of 4-methoxyphenylboronic acid.
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Herein, core-shell magnetic nanoparticles are modified with imidazolium-tagged phosphine and propylene glycol moieties and used for the stabilization of bimetallic AuCu nanoparticles. The structure and morphology of the prepared material are identified with SEM, TEM, XRD, XPS, atomic absorption spectroscopy, Fourier translation infrared spectroscopy, and a vibrating sample magnetometer. This hydrophilic magnetic bimetallic catalyst is applied in the reduction of toxic nitroarenes and reductive degradation of hazardous organic dyes such as methyl orange (MO), methyl red (MR), and rhodamine B (RhB), as well as in the degradation of tetracycline (TC). This magnetic AuCu catalyst indicated superior activity in all three mentioned reactions in comparison with its single metal Au and Cu analogs. This catalyst is recycled for 17 consecutive runs in the reduction of 4-nitrophenol to 4-aminophenol without a significant decrease in catalytic activity and recycled catalyst is characterized.
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Stable palladium (II) complexes, incorporating a double (N-benzoylthiourea) arrangement bonded to a complex heterocyclic scaffold, are used as precursors of catalytic species able to promote Suzuki-Miyaura, Mizoroki-Heck, Hiyama, Buchwald-Hartwig, Hirao and Sonogashira-Hagihara cross-coupling transformations in water. These sustainable processes are chemoselective and very versatile. The nanoparticles responsible for these catalytic reactions were analyzed and studied. Their usefulness is demonstrated after several tests and analyses. The heterogeneous character of this species in water was also confirmed.
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The reaction of arylidene-α-amino esters with electrophilic alkenes to yield Michael-type addition compounds is optimized using several phosphines as organocatalysts. The transformation is very complicated due to the generation of several final compounds, including those derived from the 1,3-dipolar cycloadditions. For this reason, the selection of the reaction conditions is a very complex task and the slow addition of the acrylic system is very important to complete the process. The study of the variation in the structural components of the starting imino ester is performed as well as the expansion of other electron-poor alkenes. The crude products have a purity higher than 90% in most cases without any purification. A plausible mechanism is detailed based on the bibliography and the experimental results. The synthesis of pyroglutamate entities, after the reduction of the imino group and cyclization, is performed in high yields. In addition, the hydrolysis of the imino group, under acidic media, represents a direct access to glutamate surrogates.
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The synthesis and biological assessment of novel multi-functionalized pyrrolidine-containing benzenesulfonamides were reported along with their antimicrobial, antifungal, CAs inhibition, and AChE inhibition as well as DNA-binding effects. The chemical structure of the compounds was elucidated by using FTIR, NMR, and HRMS. Compound 3b, which had Ki values of 17.61 ± 3.58 nM (hCA I) and 5.14 ± 0.61 nM (hCA II), was found the be the most potent CAs inhibitor. Compounds 6a and 6b showed remarkable AChE inhibition effects with Ki values 22.34 ± 4.53 nM and 27.21 ± 3.96 nM in comparison to tacrine. Compounds 6a-6c had moderate antituberculosis effect on M. tuberculosis with a MIC value of 15.62 µg/ml. Compounds had weaker antifungal and antibacterial activity in the range of MIC 500-62.5 µg/ml against standard bacterial and fungal strains. Besides these above, molecular docking studies were performed to examine and evaluate the interaction of the remarkable compounds (3b, 6a and 6b) against the current enzymes (CAs and AChE). Novel compounds gained interest in terms of enzyme inhibitory potencies. Therefore, the most potent enzyme inhibitors may be considered lead compounds to be modified for further research.Communicated by Ramaswamy H. Sarma.
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Antiinfecciosos , Anhidrasas Carbónicas , Inhibidores de la Colinesterasa/química , Bencenosulfonamidas , Acetilcolinesterasa/química , Antifúngicos/farmacología , Inhibidores de Anhidrasa Carbónica/farmacología , Inhibidores de Anhidrasa Carbónica/química , Simulación del Acoplamiento Molecular , Anhidrasa Carbónica I/metabolismo , Anhidrasa Carbónica II/metabolismo , Antiinfecciosos/farmacología , Relación Estructura-Actividad , Estructura MolecularRESUMEN
In this study, we simulate the reductive coupling (Barbier-Grignard-type) reaction of organohalides with aldehydes using a new reusable catalyst. In this regard, bimetallic alloys of NiCo encapsulated in melamine-based dendrimers (MBD) immobilized on magnetic nanoparticles symbolized as γ-Fe2O3-MBD/NiCo were designed and synthesized. The structure and properties of the catalyst were studied by a variety of techniques such as Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), energy-dispersive spectrometry (EDS) mapping, and inductively coupled plasma (ICP). The presence of NiCo nanoalloys was confirmed by XRD and XPS analysis, TEM images, and EDS mapping. Various secondary alcohols were produced in good to high yields by reductive coupling of different types of aldehydes and organohalides in the presence of HCO2K as a nonmetallic reducing agent in aqueous media catalyzed by γ-Fe2O3-MBD/NiCo. In these reactions, the high catalytic performance of γ-Fe2O3-MBD/NiCo was achieved in comparison to monometallic counterparts due to the synergistic cooperative effect of Co and Ni in the NiCo nanoalloys. Magnetic and hydrophilic properties of the catalyst facilitate the catalyst recyclability for seven runs. The reusability of γ-Fe2O3-MBD/NiCo, use of water as an environmentally friendly solvent, ease of processing, and absence of metal additives make this process an excellent choice for the reductive coupling reaction to produce secondary alcohols from aldehydes. This is the first report on these kinds of reactions using a reusable catalyst.
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Enantioconvergent catalysis has expanded asymmetric synthesis to new methodologies able to convert racemic compounds into a single enantiomer. This review covers recent advances in transition-metal-catalyzed transformations, such as radical-based cross-coupling of racemic alkyl electrophiles with nucleophiles or racemic alkylmetals with electrophiles and reductive cross-coupling of two electrophiles mainly under Ni/bis(oxazoline) catalysis. C-H functionalization of racemic electrophiles or nucleophiles can be performed in an enantioconvergent manner. Hydroalkylation of alkenes, allenes, and acetylenes is an alternative to cross-coupling reactions. Hydrogen autotransfer has been applied to amination of racemic alcohols and C-C bond forming reactions (Guerbet reaction). Other metal-catalyzed reactions involve addition of racemic allylic systems to carbonyl compounds, propargylation of alcohols and phenols, amination of racemic 3-bromooxindoles, allenylation of carbonyl compounds with racemic allenolates or propargyl bromides, and hydroxylation of racemic 1,3-dicarbonyl compounds.
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The N-tert-butanesulfinylimine group behaves as a suitable electron-withdrawing group in 1-azadienes, allowing the diastereoselective synthesis of densely substituted pyrrolidines by 1,3-dipolar cycloadditions (1,3-DCs) with azomethylene ylides. The use of Ag2CO3 as catalyst has allowed one to obtain a wide variety of proline derivatives with high regio- and diastereoselectivities. Subsequent efficient transformations provide valuable proline derivatives, some of which can be used as organocatalysts. The influence of the N-tert-butanesulfinyl group on the diastereoselectivity was studied by computational methods.
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To overcome numerous health disorders, heterocyclic structures of synthetic or natural origin are utilized, and notably, the emergence of various side effects of existing drugs used for treatment or the resistance of disease-causing microorganisms renders drugs ineffective. Therefore, the discovery of potential therapeutic agents that utilize different modes of action is of utmost significance to circumvent these constraints. Pyrrolidines, pyrrolidine-alkaloids, and pyrrolidine-based hybrid molecules are present in many natural products and pharmacologically important agents. Their key roles in pharmacotherapy make them a versatile scaffold for designing and developing novel biologically active compounds and drug candidates. This review aims to provide an overview of recent advancements (especially during 2015-2023) in the exploration of pyrrolidine derivatives, emphasizing their significance as fundamental components of the skeletal structure. In contrast to previous reviews that have predominantly focused on a singular biological activity associated with these molecules, this review consolidates findings from various investigations encompassing a wide range of important activities (antimicrobial, antiviral, anticancer, anti-inflammatory, anticonvulsant, cholinesterase inhibition, and carbonic anhydrase inhibition) exhibited by pyrrolidine derivatives. This study is also anticipated to serve as a valuable resource for drug research and development endeavors, offering significant insights and guidance.
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A magnetic nanocomposite comprising imidazolium ionic liquid and glucosamine is successfully synthesized and used for stabilization of Pd nanoparticles. This new material, Fe3O4@SiO2@IL/GA-Pd, is fully characterized and applied as a catalyst in the reduction of nitroaromatic compounds to desired amines at room temperature. Also, the reductive degradation of organic dyes such as methylene blue (MB), methyl orange (MO), and rhodamine B (RhB) is studied and compared with another previous publications. The survey of the stabilization of the palladium catalytic entities is described demonstrating the separation ability and recycling of them. In addition, TEM, XRD, and VSM analyses of the recycled catalyst confirmed its stability.
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Líquidos Iónicos , Nanopartículas del Metal , Paladio , Dióxido de Silicio , Catálisis , Fenómenos MagnéticosRESUMEN
Two supported noble metal species, gold and palladium anchored on an ionic liquid-modified Fe-based metal-organic framework (MOF), were successfully synthesized and characterized by FT-IR, XRD, TEM, XPS, SEM, EDX, and elemental mapping. The ionic liquid post-modified MOF was used for anchoring Au or Pd at ppm levels, and the resulting materials were employed as catalysts in the reduction of nitrophenol isomers, dyes, and Sonogashira-Hagihara reactions. Using the Au@Fe-MOF-IL catalyst, reduction of nitrophenol isomers, as well as the reductive degradation of dyes, e.g., methylene blue (MB), methyl orange (MO), and methyl red (MR) were performed efficiently in water. On the other hand, Pd@Fe-MOF-IL was used as an effective catalyst in the Sonogashira-Hagihara coupling reaction of aryl iodides and bromides using very low amounts of Pd. These catalysts were recycled and reused for several runs without deteriorating remarkably in catalytic performance.
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A sunlight-induced tandem air oxidation-condensation of alcohols with ortho-substituted anilines or malononitrile for the efficient synthesis of benz-imidazoles/-oxazoles/-thiazoles, or benzylidene malononitrile catalyzed by Co-isatin-Schiff-base-MIL-101(Fe) as a heterogeneous multifunctional bio-photocatalyst is reported. In these reactions, Co-isatin-Schiff-base-MIL-101(Fe) acts both as a photocatalyst, and a Lewis acid to catalyze the reaction of the in-situ formed aldehydes with o-substituted anilines or malononitrile. A significant decrease in the band gap energy and an increase in the characteristic emission of MIL-101(Fe) after functionalization with cobalt Schiff-base according to the DRS analysis and fluorescence spectrophotometry, respectively, indicate that the photocatalytic effectiveness of the catalyst is associated primarily to the synergetic influence of Fe-O cluster and Co-Schiff-base. EPR results obviously pointed out that Co-isatin-Schiff-base-MIL-101(Fe) is capable of creating 1O2 and O2â - as active oxygen species under visible light irradiation. Using an inexpensive catalyst, sunlight irradiation, air as a cost-effective and abundant oxidant, and a low amount of the catalyst with recoverability and durability in ethanol as a green solvent, make this methodology as an environmentally friendly process with energy-saving organic synthetic strategies. Furthermore, Co-isatin-Schiff-base-MIL-101(Fe) displays excellent photocatalytic antibacterial activity under sunlight irradiation against E. coli, S. aureus and S. pyogenes. Based on our knowledge, this is the first report of using a bio-photocatalyst for the synthesis of the target molecules.
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The pseudo-multicomponent reaction between propargyl amine, an aldehyde and an electron-deficient alkene is described. The C-H activation takes place thermally and allows the obtaining of cycloadducts in very good yields with high diastereoselectivities. The relative configuration is determined by X-ray diffraction analysis of the chiral molecule, obtained as a single diastereoisomer, using a chiral maleimide. A brief study of the stability of the possible ylides involved in the process is also mentioned, confirming the high diastereoselectivity observed. The high functional group density of these cycloadducts permits the synthesis of complex heterocycles. After allylation or propargylation of the pyrrolidine nitrogen atom, RCM-DA cycloaddition or cyclotrimerization with an alkyne is studied, respectively. In this last example, the resulting tetracyclic structures are of potential interest as drugs for the treatment of cystic fibrosis.
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[This corrects the article DOI: 10.3389/fchem.2022.1013349.].
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In this study, a new solar light-driven magnetic heterogeneous photocatalyst, denoted as ZnO/NiFe2O4/Co3O4, is successfully prepared. FT-IR, XPS, XRD, VSM, DRS, FESEM, TEM, EDS, elemental mapping, and ICP analysis are accomplished for full characterization of this catalyst. FESEM and TEM analyses of the photocatalyt clearly affirm the formation of a hexagonal structure of ZnO (25-40 nm) and the cubic structure of NiFe2O4 and Co3O4 (10-25 nm). Furthermore, the HRTEM images of the photocatalyst verify some key lattice fringes related to the photocatalyt structure. These data are in very good agreement with XRD analysis results. According to the ICP analysis, the molar ratio of ZnO/NiFe2O4/Co3O4 composite is obtained to be 1:0.75:0.5. Moreover, magnetization measurements reveals that the ZnO/NiFe2O4/Co3O4 has a superparamagnetic behavior with saturation magnetization of 32.38 emu/g. UV-vis DRS analysis indicates that the photocatalyst has a boosted and strong light response. ZnO/NiFe2O4/Co3O4, with band gap energy of about 2.65 eV [estimated according to the Tauc plot of (αhν)2 vs. hν], exhibits strong potential towards the efficacious degradation of tetracycline (TC) by natural solar light. It is supposed that the synergistic optical effects between ZnO, NiFe2O4, and Co3O4 species is responsible for the increased photocatalytic performance of this photocatalyst under the optimal conditions (photocatalyst dosage = 0.02 g L-1, TC concentration = 30 mg L-1, pH = 9, irradiation time = 20 min, and TC degradation efficiency = 98%). The kinetic study of this degradation process is evaluated and it is well-matched with the pseudo-first-order kinetics. Based on the radical quenching tests, it can be perceived that â¢O2 - species and holes are the major contributors in such a process, whereas the â¢OH radicals identify to have no major participation. The application of this methodology is implemented in a facile and low-cost photocatalytic approach to easily degrade TC by using a very low amount of the photocatalyst under natural sunlight source in an air atmosphere. The convenient magnetic isolation and reuse of the photocatalyst, and almost complete mineralization of TC (based on TOC analysis), are surveyed too, which further highlights the operational application of the current method. Notably, this method has the preferred performance among the very few methods reported for the photocatalytic degradation of TC under natural sunlight. It is assumed that the achievements of this photocatalytic method have opened an avenue for sustainable environmental remediation of a broad range of contaminants.
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The enantioselective 1,3-dipolar cycloaddition between imino esters and (Z)-nitroalkenes bearing a masked amino group in the ß-position was studied using several chiral ligands and silver salts. The optimized reaction conditions were directly applied to the study of the scope of the reaction. The determination of the absolute configuration was evaluated using NMR experiments and electronic circular dichroism (ECD). The reduction and hydrolysis of both groups was performed to generate in an excellent enantiomeric ratio the corresponding cis-2,3-diaminoprolinate.