Synthesis of Vicinal anti-Amino Alcohols from N-tert-Butanesulfinyl Aldimines and Cyclopropanols.

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.

First Reusable Catalyst for the Reductive Coupling Reaction of Organohalides with Aldehydes.

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.

Palladium nanoparticles supported on ionic liquid and glucosamine-modified magnetic iron oxide as a catalyst in reduction reactions.

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.

Cobalt isatin-Schiff-base derivative of MOF as a heterogeneous multifunctional bio-photocatalyst for sunlight-induced tandem air oxidation condensation process.

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 O2⋅- 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.

Corrigendum: Solar light induced photocatalytic degradation of tetracycline in the presence of ZnO/NiFe2O4/Co3O4 as a new and highly efficient magnetically separable photocatalyst.

[This corrects the article DOI: 10.3389/fchem.2022.1013349.].

Solar light induced photocatalytic degradation of tetracycline in the presence of ZnO/NiFe2O4/Co3O4 as a new and highly efficient magnetically separable photocatalyst.

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 •O2 - species and holes are the major contributors in such a process, whereas the •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.

ZnCo2O4/g-C3N4/Cu nanocomposite as a new efficient and recyclable heterogeneous photocatalyst with enhanced photocatalytic activity towards the metronidazole degradation under the solar light irradiation.

In this study, ZnCo2O4/g-C3N4/Cu is synthesized as a new and highly effectual solar light-driven heterogeneous photocatalyst. The prepared photocatalyst is characterized using FT-IR, XRD, XPS, DRS, FESEM, TEM, EDS, and elemental mapping techniques. The performance of ZnCo2O4/g-C3N4/Cu is studied towards the metronidazole (MNZ) degradation under solar light irradiation. The kinetics of MNZ degradation and efficacy of the operational parameters comprising the initial MNZ amount (10-30 mg L-1), photocatalyst dosage (0.005-0.05 g L-1), pH (3-11), and contact time (5-30 min) on the MNZ degradation process are investigated. Surprisingly, the ZnCo2O4/g-C3N4/Cu nanocomposite presents a privileged photocatalytic performance towards the MNZ degradation under solar light irradiation. The enhanced photocatalytic activity of this photocatalyst can be ascribed to the synergistic optical effects of ZnCo2O4, g-C3N4, and Cu. The value of band gap energy for ZnCo2O4/g-C3N4/Cu is estimated to be 2.3 eV based on the Tauc plot of (αhν)2 vs. hν. The radical quenching experiments confirm that the superoxide radicals and holes are the principal active species in the photocatalytic degradation of MNZ, whereas the hydroxyl radicals have no major role in such degradation. The as-prepared photocatalyst is simply isolated and recycled for at least eight runs without noticeable loss of the efficiency. Using the natural sunlight source, applying a very low amount of the photocatalyst, neutrality of the reaction medium, short reaction time, high efficiency of the degradation procedure, utilizing air as the oxidant, low operational costs, and easy to recover and reuse of the photocatalyst are the significant highlights of the present method. It is supposed that the current investigation can be a step forward in the representation of an efficacious photocatalytic system in the treatment of a wide range of contaminated aquatic environments.

A novel base-metal multifunctional catalyst for the synthesis of 2-amino-3-cyano-4H-chromenes by a multicomponent tandem oxidation process.

A novel base-metal multifunctional nanomagnetic catalyst is prepared by the immobilization of tungstate anions onto γ-Fe2O3 supported with imidazolium moieties. The (γ-Fe2O3-Im-Py)2WO4 was fully characterized using FT-IR, XPS, TEM, FESEM, ICP, TGA, VSM and XRD and used as a multifunctional heterogeneous catalyst for the synthesis of 2-amino-3-cyano-4H-chromenes via a multicomponent tandem oxidation process starting from alcohols under solvent-free conditions. During this process, tungstate catalyzes the oxidation of a wide range of alcohols in the presence of TBHP as a clean source. The in-situ formed aldehydes are condensed with malononitrile and ß-dicarbonyl compounds/naphthols/4-hydroxycumarin through promotion by pyridine and imidazolium moieties of the catalyst. By this method, a variety of 2-amino-3-cyano-4H-chromenes are generated in good to high yields from alcohols as inexpensive and easily available starting materials. The catalyst is recovered easily by the aid of an external magnetic field and reused in five successive runs with insignificant decreasing activity.

A new nanomagnetic Pd-Co bimetallic alloy as catalyst in the Mizoroki-Heck and Buchwald-Hartwig amination reactions in aqueous media.

A Pd-Co bimetallic alloy encapsulated in melamine-based dendrimer supported on magnetic nanoparticles denoted as γ-Fe2O3@MBD/Pd-Co was synthesized by a facile co-complexation-reduction method and characterized sufficiently. The catalytic evaluation of γ-Fe2O3@MBD/Pd-Co showed promising results in the Mizoroki-Heck and Buchwald-Hartwig amination reactions of various iodo-, bromo- and challenging chloroarenes in aqueous media. The synergetic cooperative effect of both Pd and Co and dispersion of the catalyst in water due to the encapsulation of γ-Fe2O3 by melamine-based dendrimer lead to high catalytic performance compared with the monometallic counterparts. The dispersion of the magnetic catalyst also facilitates the recovery and reuse of the catalyst by ten consecutive extraction and final magnetic isolation with no loss of catalytic activity, keeping its structure unaltered.

Tandem imine formation via auto-hydrogen transfer from alcohols to nitro compounds catalyzed by a nanomagnetically recyclable copper catalyst under solvent-free conditions.

A direct imination reaction was developed by tandem reaction of alcohols and nitro compounds in the presence of Cu-isatin Schiff base-γ-Fe2O3 as a nanomagnetically recyclable catalyst under solvent-free conditions. By this method, various imines were prepared in good to high yields from one-pot reaction of various alcohols (primary aromatic and aliphatic) and nitro compounds (aromatic and aliphatic) via an auto-hydrogen transfer reaction. Use of an inexpensive and easily reusable catalyst, without requiring any additives or excess amounts of benzyl alcohol as the reaction solvent are the other advantages of this method. This catalytic system has the merits of cost effectiveness, environmental benignity, excellent recyclability and good reproducibility.

New Nanomagnetic Heterogeneous Cobalt Catalyst for the Synthesis of Aryl Nitriles and Biaryls.

Cobalt nanoparticles immobilized on magnetic chitosan (Fe3O4@CS-Co) have been prepared. They were identified using various techniques such as Fourier-transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, thermogravimetric analysis, vibrating sample magnetometry, X-ray photoelectron spectroscopy, and inductively coupled plasma atomic emission spectroscopy analysis and applied efficiently as a cobalt catalyst in the cyanation and fluoride-/palladium-free Hiyama reactions of different types of aryl halides employing K4[Fe(CN)6]·3H2O and triethoxyphenylsilane, respectively. After each reaction, the catalyst was isolated and reused for the second run. The catalytic activity of the catalyst was not lost apparently even after five runs. No considerable changes in its chemical structure and morphology were observed. It is worth to note that in this paper, the cobalt catalyst has been used for the first time for the cyanation of aryl halides.

A new bifunctional heterogeneous nanocatalyst for one-pot reduction-Schiff base condensation and reduction-carbonylation of nitroarenes.

In this work, synthesis of Pd-NHC-γ-Fe2O3-n-butyl-SO3H and its activity as a bifunctional heterogeneous nanocatalyst containing Pd-NHC and acidic functional groups, are described. This newly synthesized nanomagnetic catalyst is fully characterized by different methods such as FT-IR, XPS, TEM, VSM, ICP and TG analysis. At first, the catalytic activity of Pd-NHC-γ-Fe2O3-n-butyl-SO3H is evaluated for the reduction of nitroarenes in aqueous media using NaBH4 as a clean source of hydrogen generation at ambient temperature. Using the promising results obtained from the nitroarene reduction, this catalytic system is used for two one-pot protocols including reduction-Schiff base condensation and reduction-carbonylation of various nitroarenes. In these reactions the in situ formed amines are further reacted with aldehydes to yield imines or carbonylated to amides. The desired products are obtained in good to high yields in the presence of Pd-NHC-γ-Fe2O3-n-butyl-SO3H as a bifunctional catalyst. The catalyst is reused with the aid of a magnetic bar for up to six consecutive cycles without any drastic loss of its catalytic activity.