An efficient and environmentally sustainable domino protocol for the synthesis of structurally diverse spiroannulated pyrimidophenazines using erbium doped TiO2 nanoparticles as a recyclable and reusable heterogeneous acid catalyst

An efficient and environmentally sustainable domino protocol has been presented for the synthesis of structurally diverse spiroannulated pyrimidophenazines involving a four component reaction of 2-hydroxynaphthalene-1,4-dione, benzene-1,2-diamine, cyclic ketones and amino derivatives in the presence of erbium doped TiO₂ nanoparticles as a recyclable and reusable heterogeneous acid catalyst. The present synthetic protocol features mild reaction conditions with operational simplicity, excellent yield with high purity, short reaction time and high atom economy with the use of a recoverable and reusable environmentally sustainable heterogeneous catalyst.

An efficient and environmentally sustainable domino protocol has been presented for the synthesis of structurally diverse spiroannulated pyrimidophenazines using erbium doped TiO₂ nanoparticles as a recyclable and reusable heterogeneous acid catalyst.     

Aluminium based binary catalytic system for the solvent free conversion of CO2 to carbonates with high activity and selectivity

An easily prepared and low-cost aluminium based metal complex catalyst was prepared using kojic acid (Hkoj) as a ligand, and this developed oxo-coordinated Al(koj)₃ complex showed high activity and selectivity for the CO₂ fixation reaction with epoxides under mild conditions without any organic solvents. Various cyclic carbonates were obtained in excellent yields (up to 99%). This stable catalytically active Al(koj)₃ has strong Lewis acidity for the activation of epoxides, and meanwhile the hydroxy group in Al(koj)₃ may play a role in boosting the catalytic activity through possible hydrogen bonding interactions with the epoxide.

A multifunctional aluminum based complex was employed as an efficient and recyclable catalyst for the synthesis of carbonates from CO₂ and epoxides.     

Recyclable iron(ii) caffeine-derived ionic salt catalyst in the Diels–Alder reaction of cyclopentadiene and α,β-unsaturated N-acyl-oxazolidinones in dimethyl carbonate

Iron(ii) triflate was used in combination with caffeine-derived salts as recyclable catalysts for the Diels–Alder reaction run in dimethyl carbonate (DMC) as a green solvent. The catalyst was prepared as an ionic salt from a xanthinium salt and Fe(OTf)₂. Various substrates including α,β-unsaturated carbonyl and N-acyloxazolidinone derivatives were reacted with cyclopentadiene using this recyclable catalyst. The use of a low catalyst loading (1 mol%) afforded high yields (up to 99%) of the corresponding cycloadducts. The recycling and the efficiency of the catalyst were demonstrated for several runs.

Iron(ii) triflate was used in combination with caffeine-derived salts as recyclable catalysts for the Diels–Alder reaction run in dimethyl carbonate (DMC) as a green solvent.     

Synthesis of benzo[4,5]imidazo[1,2-a]pyrimidines and 2,3-dihydroquinazolin-4(1H)-ones under metal-free and solvent-free conditions for minimizing waste generation

Brønsted acidic ionic liquid was found to be an efficient and recyclable catalyst for the synthesis of benzo[4,5]imidazo[1,2-a]pyrimidines and 2,3-dihydroquinazolin-4(1H)-ones. The reactions proceeded smoothly with a broad scope of substrates providing the expected products in good to excellent yields under an atom-economical pathway. The low-cost recyclable catalyst, metal- and solvent-free conditions, and the ease of product isolation are the highlighted advantages in solving the issue of trace metal contamination in synthesized pharmaceuticals.

A facile, efficient, and atom-economic method for preparing benzo[4,5]imidazo[1,2-a]pyrimidines and 2,3-dihydroquinazolin-4(1H)-ones under metal- and solvent-free condition has been developed.     

Direct synthesis of amides and imines by dehydrogenative homo or cross-coupling of amines and alcohols catalyzed by Cu-MOF

Oxidative dehydrogenative homo-coupling of amines to imines and cross-coupling of amines with alcohols to amides was achieved with high to moderate yields at room temperature in THF using Cu-MOF as an efficient and recyclable heterogeneous catalyst under mild conditions. Different primary benzyl amines and alcohols could be utilized for the synthesis of a wide variety of amides and imines. The Cu-MOF catalyst could be recycled and reused four times without loss of catalytic activity.

Oxidative dehydrogenative homo or cross-coupling of amines with alcohols to imines and amides was achieved with high to moderate yields at room temperature using Cu-MOF as an efficient and recyclable heterogeneous catalyst.     

One-pot synthesis of amides via the oxidative amidation of aldehydes and amines catalyzed by a copper-MOF

An efficient method for the oxidative amidation of aldehydes with primary aromatic and aliphatic amines has been developed for the synthesis of a wide variety of amides using inexpensive Cu₂(BDC)₂DABCO (Cu-metal–organic framework [MOF]) as a recyclable heterogeneous catalyst, and N-chlorosuccinimide and aqueous tert-butyl hydroperoxide as oxidants in acetonitrile. This amidation reaction is operationally straightforward and provides secondary amides in good yields in most cases, utilizing inexpensive and readily available reagents under mild conditions.

A method for oxidative amidation of aldehydes with primary amines was developed to synthesise a variety of amides using Cu₂(BDC)₂DABCO (Cu-MOF) as a recyclable heterogeneous catalyst, and N-chlorosuccinimide and aqueous tert-butyl hydroperoxide as oxidants in acetonitrile.     

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.

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.     

Production of cellulose nanofibrils and films from elephant grass using deep eutectic solvents and a solid acid catalyst

A new strategy was developed to produce cellulose nanofibrils (CNFs) and films from raw elephant grass using deep eutectic solvents and a recyclable spent coffee-derived solid acid (SC-SO₃H) catalyst with assistance of ultrasonic disintegration and a suction filtration film forming method. The effects of a solid acid and reused solid acid were comprehensively studied by comparing with catalyst-free conditions and using sulfuric acid as the catalyst. The CNF fibers obtained from this novel SC-SO₃H catalyst method showed the longest fiber length. The corresponding films achieved the strongest tensile strength of 79.8 MPa and the elongation at break of 13.6%, and best thermostability. In addition, the performance of CNFs and films prepared by the fourth recovered SC-SO₃H-4 catalyst was close to that obtained with the first use. The SC-SO₃H could be reused by a simple decantation method, meaning this novel method has the potential for green and sustainable preparation of CNFs and films.

A new strategy was developed to produce cellulose nanofibrils and films from elephant grass using deep eutectic solvents and a recyclable solid acid catalyst with assistance of ultrasonic disintegration and a suction filtration film forming method.     

Sulfonic-acid-functionalized carbon fiber from waste newspaper as a recyclable carbon based solid acid catalyst for the hydrolysis of cellulose

Waste newspaper is one of the most common cellulosic materials. Therefore, effective utilization of this commonly available biomass resource to prepare high-value carbon-based solid acid catalysts is an interesting and meaningful task. In this study we propose a new route for waste newspaper valorization, in which sulfonic-acid-functionalized carbon fiber can be directly produced from waste newspaper as a recyclable carbon based solid acid catalyst (WCSA) for the hydrolysis of cellulose. The as-prepared sulfonic-acid-functionalized carbon fiber contained –SO₃H, –COOH, and phenolic –OH groups and exhibited good catalytic activity for the hydrolysis of cellulose. WCSA prepared under sulfonation conditions at a temperature of 100 °C and for a duration of 10 h has a higher sulfonic acid content. A total reducing sugars (TRS) yield of 58.2% was obtained with a catalyst/microcrystalline cellulose (MCC) ratio of 4 at 150 °C using a reaction time of 6 h. The recycling performance of the WCSA catalyst indicated that the TRS remained almost stable for five cycles during the hydrolysis of cellulose.

Waste newspaper is one of the most common cellulosic materials.     

Influence of the acidity of solid catalyst HSO3-ZSM-5 on the hydrolysis of pretreated corncob

This work aimed to investigate the application of a solid acid catalyst, a replacement for mineral acids or enzymes, to biomass conversion for further applications. Sulfonated zeolite, HSO₃-ZSM-5, was successfully synthesized and characterized by several analysis techniques. The obtained catalyst showed high activity and efficiency in the hydrolysis of pretreated corn cob. Moreover, the acidity of the zeolite product positively influenced the biomass conversion. The influences of reaction parameters such as catalyst loading, reaction time and temperature on the hydrolysis were also established. Under suitable conditions, a hydrolysis yield of ∼54% was achieved. This recyclable solid acid catalyst provided a promising potential for applications in many industrially important hydrolysis processes of biomass.

The influence of acidity of HSO₃-ZSM-5 zeolite on biomass hydrolysis was investigated.     

Phosphotungstic acid impregnated niobium coated superparamagnetic iron oxide nanoparticles as recyclable catalyst for selective isomerization of terpenes

Conversion efficiency as high as 80–100% and 50% selectivity for camphene and limonene was achieved with low production of polymeric byproducts (18–28%), easy recovery with a magnet and reuse for up to five cycles maintaining similar activity and distribution of products, using a new magnetically recyclable catalyst based on niobium oxide coated on superparamagnetic iron oxide nanoparticles (SPION) impregnated with phosphotungstic acid (HPW). The catalyst was demonstrated to be effective in the selective conversion of alpha and beta-pinenes into valuable terpenes, under ultrasonic probe activation and with toluene as solvent. A unique synergic effect between the components generating more active and selective catalytic sites was demonstrated, indicating that the SPION covered with 30 wt% of Nb₂O₅ gives the best performance when impregnated with HPW as co-catalyst. The materials were fully characterized by XRD, EDX, XPS, TEM, BET, VSM and FTIR.

Conversion efficiency as high as 80–100% and 50% selectivity for camphene and limonene was achieved with low production of polymeric byproducts (18–28%), using a new magnetically recyclable catalyst – SPION-Nb30@HPW.     

Cu-metal organic frameworks (Cu-MOF) as an environment-friendly and economical catalyst for one pot synthesis of tacrine derivatives

The present work describes the catalytic activity of Cu-MOF for the one-pot synthesis of tacrine derivatives via a four-component reaction of 2-hydroxynaphthalene-1,4-dione, aldehydes, malononitrile and cycloketones in the presence of AlCl₃. The structure of the synthesized compound is confirmed by ¹H NMR, ¹³C NMR, IR, and MASS. The catalyst prepared under pressure is characterized by powder X-ray diffraction and SEM. The noteworthy advantages of this procedure include its broad substrate scope, high yields up to 93%, atom economy, using readily available starting materials and a powerful recyclable nano catalyst. Additionally, there is no need to use column chromatography for purifying products so, it has the potential for large-scale applications in pharmaceutical industries. Another advantage of this method is the ability to recycle the catalyst up to 3 times and reuse it.

The present work describes the catalytic activity of Cu-MOF for the one-pot synthesis of tacrine derivatives via a four-component reaction of 2-hydroxynaphthalene-1,4-dione, aldehydes, malononitrile and cycloketones in the presence of AlCl₃.     

Novel biocompatible core/shell Fe3O4@NFC@Co(ii) as a new catalyst in a multicomponent reaction: an efficient and sustainable methodology and novel reusable material for one-pot synthesis of 4H-pyran and pyranopyrazole in aqueous media

Today, due to the developing need for inexpensive catalysts, recyclable magnetic nanocatalysts immobilized on polysaccharides possess many advantages over classical heterogeneous catalysts. However, cellulose has been an appealing material in catalysis science and technology. In this work, by controlling the interaction between the inorganic complexes and the support material, we designed a high activity nanostructured combination of a magnetic nanoparticle Fe₃O₄@NFC@Co(ii) terminated complex as a multi-nuclear catalyst. This protocol involves an environment friendly approach using cobalt acetate. The magnetic nanostructure Fe₃O₄@NFC@Co(ii) can be used as a novel, green, and a powerful catalyst that demonstrates a short reaction time, high yield and easy procedure for the cascade Knoevenagel–Michael-cyclocondensation reaction for the one-pot synthesis of 4H-pyrans and pyranopyrazoles. The superparamagnetic nanocomposite could be conveniently separated by using an external magnet. Moreover, the catalyst could be reused at least five times in new reaction runs without a noticeable loss of activity. The prepared catalyst was characterized by FT-IR, XRD, VSM, FESEM, EDAX, TEM, ICP, and TGA techniques. The experiments were achieved with good yields and implied that the catalytic method was effective and convenient for heterocyclic synthesis.

Today, due to the developing need for inexpensive catalysts, recyclable magnetic nanocatalysts immobilized on polysaccharides possess many advantages over classical heterogeneous catalysts.     

Heteroatom-doped nanoporous carbon from recyclable Pueraria lobata and its dual activities for oxygen reduction and hydrogen evolution reactions

Many efficient and non-precious metal catalysts for oxygen reduction or hydrogen evolution reactions have been developed, but bifunctional catalysts for both oxygen reduction reaction and hydrogen evolution reactions are seldom reported despite their advantages. Herein, we designed the bulk preparation of heteroatom-doped nanoporous carbon catalysts using widely available and recyclable Pueraria lobata powder as the carbon source. The typical product was N, P and Fe Tri-doped nano-porous carbon (N,P,Fe-NPC) with high surface area (BET surface area of 776.68 m² g⁻¹ and electrochemical surface area of 55.0 mF cm⁻²). The typical N,P,Fe-NPC sample simultaneously exhibited high activities for oxygen reduction and hydrogen evolution reactions. Because of the high surface area and the tri-doping of N, P and Fe elements, the prepared material may have applications in other fields such as gas uptake, sensors, sewage treatment, and supercapacitors. The suggested approach is low-cost, simple and readily scalable.

The bulk preparation of an N, P and Fe Tri-doped nano-porous carbon sample using recyclable Pueraria powder, which exhibits dual activities.     

Synergistic advanced oxidation process for enhanced degradation of organic pollutants in spent sulfuric acid over recoverable apricot shell-derived biochar catalyst

The sulfuric acid-based alkylation process, which leads the industrial application market, still struggles with effectively removing a large number of organic pollutants from hazardous spent sulfuric acid. A synergistic advanced oxidation process was constructed to degrade the organic pollutants with H₂O₂ and sodium persulfate as the synergistic oxidants and apricot shell-derived biochar (OBC) as the catalyst. Taking the total organic carbon (TOC) and the color scale as the indices, the effects of critical experimental factors, i.e., reaction temperature, initial oxidant concentration, catalyst dosage, and aeration rate, were optimized. The results showed that the removal rates of TOC and the color of the spent sulfuric acid reached ∼91% and 96.6%, respectively, after 150 min under the optimum conditions. Besides, the efficient and low-cost OBC catalyst developed in this study could be continuously used for at least four times with about 75% TOC removal and 80% color removal, exhibiting favorable stability and good resistance to acid corrosion. Further study confirmed that the SO₄−˙ and ˙OH radicals generated in the synergistic advanced oxidation process strengthened the degradation and elimination of organic pollutants. The synergistic advanced oxidation process could provide a feasible insight for spent sulfuric acid treatment.

A synergistic advanced oxidation process was constructed to degrade the organic pollutants in spent sulfuric acid with apricot shell-derived biochar as the catalyst. It realized the effect of treating waste with waste.     

Combined experimental and computational study of Al2O3 catalyzed transamidation of secondary amides with amines

Amides are the most extensively used substances in both synthetic organic and bioorganic chemistry. Unfortunately, the traditional synthesis of amides suffers from some important drawbacks, including low atom efficiency, high catalyst loading, separation of products from the reaction mixture and production of byproducts. Al₂O₃ is an amphoteric catalyst that activates the carbonyl carbon of the secondary amide group and helps the C–N cleavage of the reactant amide group by attacking the N–H hydrogen. By using the concepts of amphoteric properties of Al₂O₃, amides were synthesized from secondary amides and amines in the presence of triethylamine solvent. Several aliphatic and aromatic amines were used for the transamidation of N-methylbenzamide in the presence of the Al₂O₃ catalyst. Moreover, using the Gaussian09 software at the DFT level, HUMO, LUMO and the intrinsic reaction coordinates (IRCs) have also been calculated to find out the transition state of the reaction and energy. In this study, five successful compounds were synthesized by the transamidation of secondary amides with amines using a reusable Al₂O₃ catalyst. The catalyst was reused several times with no significant loss in its catalytic activity. The products were purified by recrystallization and column chromatography techniques. This catalytic method is effective for the simultaneous activation of the carbonyl group and N–H bond by using the Al₂O₃ catalyst.

Amides are the most extensively used substances in both synthetic organic and bioorganic chemistry.     

Dendritic structured palladium complexes: magnetically retrievable,highly efficient heterogeneous nanocatalyst for Suzuki and Heck cross-coupling reactions

The recyclable nanomagnetic Pd-complex PAMAM G₀-Pd@γ-Fe₂O₃ is reported for catalytic C–C cross-coupling reactions of challenging substrates. Mainly, a great variety of aryl chlorides can be used as substrates for Suzuki–Miyaura and Mizoroki–Heck reactions under mild reaction conditions (60–90 °C) and low catalyst loading (<1 mol% Pd) in aqueous media. The presence of numerous polar groups in the polymer matrix increases the solubility of the catalyst in water, thus facilitating its operation in aqueous environments. The immobilization of the catalyst on the surface of a magnetic platform allows its effective recovery and reuse without significant loss of catalytic activity for at least six cycles with total leaching of <1% palladium metal, meeting the requirements for acceptable metal residues in the pharmaceutical industry.

The recyclable nanomagnetic Pd-complex PAMAM G₀-Pd@γ-Fe₂O₃ is reported for catalytic C–C cross-coupling reactions of challenging substrates.     

Simple organocatalyst component system for asymmetric hetero Diels–Alder reaction of isatins with enones

A simple two catalyst component system consisting of primary β-amino alcohols as a catalyst and amino acids as a co-catalyst put together works as an efficient organocatalyst system in the hetero Diels–Alder reaction of isatins with enones to afford the chiral spirooxindole–tetrahydropyranones in good chemical yields and stereoselectivities (up to 86%, up to 85 : 15 dr., up to 95% ee).

A simple two catalysts component system of β-amino alcohols (catalyst) and amino acids (co-catalyst) works as an efficient organocatalysts in hetero Diels–Alder reaction of isatins with enones to afford chiral spirooxindole-tetrahydropyranones.     

Catalyst free N-formylation of aromatic and aliphatic amines exploiting reductive formylation of CO2 using NaBH4

Herein, we report a sustainable approach for N-formylation of aromatic as well as aliphatic amines using sodium borohydride and carbon dioxide gas. The developed approach is catalyst free, and does not need pressure or a specialized reaction assembly. The reductive formylation of CO₂ with sodium borohydride generates formoxy borohydride species in situ, as confirmed by ¹H and ¹¹B NMR spectroscopy. The in situ formation of formoxy borohydride species is prominent in formamide based solvents and is critical for the success of the N-formylation reactions. The formoxy borohydride is also found to promote transamidation reactions as a competitive pathway along with reductive functionalization of CO₂ with amine leading to N-formylation of amines.

Herein, we report a sustainable approach for N-formylation of aromatic as well as aliphatic amines using sodium borohydride and carbon dioxide gas.     

Heteropolyacid ionic liquid heterogeneously catalyzed synthesis of isochromans via oxa-Pictet–Spengler cyclization in dimethyl carbonate

A recyclable and efficient heterogeneous, green catalyst based on the synthesis of Keggin-type polyoxometalate (H₃PMo₁₂O₄₀) and vitamin B1 analogue 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazol-3-ium (HEMT), i.e., [HEMTH]H₂[PMo₁₂O₄₀] was prepared. Oxa-Pictet–Spengler cyclization of arylethanols and aldehydes were catalyzed to afford various substituted isochromans in moderate conditions with excellent yields using dimethyl carbonate (DMC) as a green solvent. Furthermore, this protocol was applicable in a gram-scale reaction, and the catalyst could be recycled eight times without significant loss of activity.

An efficient heterogeneous and green catalyst [HEMTH]H₂[PMo₁₂O₄₀] was prepared to catalysis the oxa-Pictet–Spengler cyclization of arylethanols and aldehydes to afford isochromans with excellent yields using dimethyl carbonate as a green solvent.