Magnetic DL-methionine grafted to chitosan by EDTA linker nanomaterial: a highly efficient multifunctional organocatalyst for the synthesis of highly substituted imidazole derivatives under green conditions

Magnetic DL-methionine grafted to chitosan by EDTA linker nanomaterial: a highly efficient multifunctional organocatalyst for the synthesis of highly substituted imidazole derivatives under green conditions | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Magnetic DL-methionine grafted to chitosan by EDTA linker nanomaterial: a highly efficient multifunctional organocatalyst for the synthesis of highly substituted imidazole derivatives under green conditions Mohammad Dohendou, Mohammad G. Dekamin, Zahra Dehnamaki, Danial Namaki, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4619378/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract In this research, a novel protocol for the synthesis of imidazole derivatives with various substitutions has been investigated in the presence of a new and highly effective magnetic decorated DL-methionine amino acid grafted onto the chitosan backbone by using EDTA linker (CS − EDTA − MET@Fe 3 O 4 ) under green chemistry conditions. The CS − EDTA − MET@Fe 3 O 4 nanocomposite was properly characterized by using FTIR, EDX, XRD, FESEM, TGA and VSM spectroscopic, microscopic, or analytical methods. The CS − EDTA − MET@Fe 3 O 4 nanocomposite was used as a highly efficient heterogeneous organocatalyst for the synthesis of a wide range of three- and four-substituted imidazole derivatives, as an important pharmaceutical scaffold, through multicomponent reactioins (MCRs) strategy. The CS − EDTA − MET@Fe 3 O 4 multifunctional nanocatalyst exhibited high catalytic activity, selectivity, and stability to promote the reactions of benzoin or benzyl, different aldehyde derivatives, and ammonim acetate as well as aromatic or aliphatic amine derivatives in EtOH as green solvent. Key advantages of the present protocol are high to excellent yields, the use of a low loading renewable, bio-based and biodegredable chitosan- as well as amino acid-based nanomaterial, and simple procedure for the preparation of CS − EDTA − MET@Fe 3 O 4 nanomaterial and synthesis of a wide range of imoidazole derivatives. In addition, the catalyst's properties, including its magnetic properties and appropriate surface area characteristicscontribute to its excellent catalytic performance. Fuerthermore, the CS − EDTA − MET@Fe 3 O 4 nanocatalyst can be used for up to six cycles for the preparation of imidazole derivatives with only a slight decrease in its catalytic activity. Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Introduction Nanomaterials are being explored and utilized across various sectors such as biomedicine and nanomedicine, energy storage and transformation, environment remediation and water purification, catalysis, etc 1–5 . In this context, nano-ordered catalytic systems have received great interest in recent years due to their high activity resulting from high surface to volume ratio and appropriate dispersion of active sites, shape-selectivity and quantum size effect as well as the ability to be recycled and reused repetitively to address the gap between the classic homogenous and bulk heterogeneous catalysts and making a bridge between these active research fields 4,6–25 . This impact can be intensified when biopolymers and their modified forms, as the heterogeneous version of organocatalysts, come to play and add more advantages to the designed nano-ordered catalytic systems in terms of zero or low toxicity as well as their biodegradability after retirement 21,26–32 . Furthermore, multifunctional nanocatalysts are very beneficial to promote multi-step reaction requiring same or different active sites in a single pot. All these criteria make the processes greener and more sustainable, especially for atom-/step economic multicomponent reactions (MCRs) 28,31,33–36 . Nowadays, MCRs are effective tools and procedures to prepare complex scaffolds, which are important in the fine chemical industry including pharmaceutical, dyes and color industries, etc 37–42 . The invention of MCRs goes back to middle of 19th century by pioneer scientists including Strecker 28,43 , Hantzsch 44,45 , Biginelli 39,46 . MCRs are convergent reactions, in which more than two commercially accessible precursors have been mixed together to react and form important acyclic or heterocyclic products with high bond formation index (BFI) 47–53 . In recent decades, MCRs have emerged as an interesting tool that allows the simple synthesis of complex molecules in one-pot synthesis, without separating and purifying intermediates; therefore, it leads to cost, time and energy reduction 54–58 . However, MCRS generally requires homogenous or heterogeneous catalytic systems to afford high to excellent yields in shorter reaction times, which are important factors in designing of new processes in the pharmaceutical industry. Hence, (MCRs) in combination with nano-ordered catalysts have received significant interest for the synthesis of many pharmaceuticals or other fine chemicals in recent years 10–14,59-64 . Due to importance of MCRs in different fields of science including chemical and pharmaceutical sectors, the application of a novel, robust and convenient catalytic methods is demanded. Therefore, to cover the principles of GC in terms of less hazardous materials, inexpensive methods, effective and high yields protocols, a variety of catalytic systems have been considered recently 65–74 . Among these, due to provide magnetic properties as support for different organic transformations as well as their proper surface area and nanomagnetic characteristics, magnetic nanoparticles have received scientific attention in different fields of catalytic systems including Bronsted acid/or base, traditional metal, organo- and enzymatic catalysis reactions. As a result, chemical stability, being specifically robust as well as availability with a naturally low toxicity and cost has made them efficient replacements to other known catalyst supports especially silica and alumina 20,31,33,34,75–117 . Imidazole derivatives have occupied a unique position in the heterocyclic chemistry. They are N -containing heterocyclic ring that possess versatile properties in the both chemical and pharmaceutical sectors 118 . The imidazole scaffold is existing in the several important natural products including purine, histamine, histidine, and nucleic acid. Having both polar and ionizable properties improves the pharmacokinetic characteristics and make imidazole heterocycles an important group that can cover an extensive spectrum of biologically active materials comprising antibacterial, anticancer, antitubercular, antifungal, analgesic, and anti-HIV compounds 27,38,45,119–122 ( Fig. 1 ) . Additionally, highly-substituted 1,3-dialkylimidazoles have shown high potential in the form of ionic liquids, as green solvents, or precursors of N -heterocyclic carbens (NHCs). The NHCs are of interest as effective organocatlysts or ligands in coordination chemistry recently 123–126 . Hence the advantages and vast applications of imidazole moiety in different fields of science highlights the necessity of designing and performing well-organized preparing procedures for the synthesis of corresponding highly substituted derivatives. In this regard, the MCRs of benzyl or benzoin with aldehydes, and primary amines or ammonium acetate is one of the most convenient protocols for synthesis of multi-substituted imidazole derivatives. 127–130 Following this issue, numerous heterogenous or homogenous catalytic systems including ZSM-11 or HY zeolite, dimethylpyridinium trinitromethanide, 3-picolinic acid, silica sulfuric acid, ZrO 2 -Al 2 O 3 , ZrO 2 -β-cyclodextrin, nano-Al-MCM-41, triethylammonium acetate as an ionic liquid, I 2 , Kegin-type hetero polyacids, chitosan-coated Fe 3 O 4 nanoparticles, Fe 3 O 4 -PEG-Cu, Bohemite nanoparticles, silica choloride, 2,6-pyromellitic diamide–diacid bridged mesoporous organosilica nanospheres, (N 2 H 5 ) 2 SiF 6 , magnetic polyborate nanoparticles 131 and Fe 3 O 4 /SiO 2 decorated trimesic acid-melamine have been employed for the multi-component synthesis of desired imidazole derivatives 70,100,132–136 . Although these mentioned methods have several advantages, they suffer from several disadvantages such as using hazardous or expensive reagents, pollution created during the catalyst preparation, low stability or recyclability of the catalysts and also low yields of the desired products, long reaction times and difficult work-up procedures. Therefore, designing and preparation of the productive, environmentally-benign and inexpensive methods for the synthesis of multi-substituted imidazoles would be very demanded 54 . In this research and in continuing our previous works 29,30,40 , we have reported a novel sustainable green nanomagnetic catalytic system (CS-EDTA-MET@Fe 3 O 4 catalyst, 1 ) based on modified naturally-occurring biopolymeric chitosan, by using methionine amino acid through grafting of EDTA dianhydride linker followed by Fe 3 O 4 decoration. The catalyst ( 1 ) was examined in both 3- and 4-components reactions for successful synthesis of corresponding imidazole derivatives in high to excellent yields and short reaction time ( Fig. 2 ) . Results and Discussion The prepared CS-EDTA-MET@ Fe 3 O 4 organocatalyst ( 1 ) was characterized using various suitable techniques including FT-IR, FESEM, XRD, TGA and EDS. Figure 3 shows the FT-IR spectra of chitosan ( a ) and CS-EDTA-MET@Fe 3 O 4 ( 1 , b ). According to Fig. 3 a, the absorption bands at 3100–3444 cm − 1 are attributed to the stretching vibration of both O–H and N–H bonds of amine groups. Also, absorption band at 2923 cm − 1 belongs to the stretching vibration of C–H aliphatic bonds. As shown in Fig. 3 b, the broad absorption bands at 2400–3400 cm − 1 are attributed to the stretching vibration of COOH functional groups. The absorption band at 588 is attributed to the Fe‒O bonds. Other functional groups including ester and amide are also observed in the FTIR spectrum but in lower intensities. Figure 4 shows the EDS analysis related to the CS-EDTA-MET@ Fe 3 O 4 organocatlyst ( 1 ), which confirms the presence of C, O, N, S and Fe elements in its structure. Also, the EDS mapping images shows the uniform particle distribution in the nanomaterial texture. FESEM images of CS-EDTA-MET @Fe 3 O 4 nanomaterial ( 1 ) are shown in Fig. 5 . The FESEM images of the structure of CS-EDTA-MET @Fe 3 O 4 shows that the morphology of chitosan has changed from wide regular sheets to smaller irregular particles, which confirms the formation of the desired format. Also, these particles have a uniform dispersion and average particle size of 20–55 nm. Using thermogravimetric analysis (TGA), the thermal stability of the prepared catalyst ( 1 ) was investigated in the temperature range of 50–1000°C. As shown in Fig. 6 , two weight loss steps were observed between 250 and 400°C. Since the pristine chitosan is degraded at 200–220°C 23 , This degradation at the temperature range of 250–400°C indicates that DL-methionine is grafted properly to the chitosan backbone through EDTA linker, which affects the thermal stability of the chitosan and its degradation takes place at a higher temperature. Another weight loss can be seen from 400–500°C, which is related to the total decomposition of the polymeric chain and carbon residue. The curve slope remains approximately constant from 500–1000°C. This phenomenon shows the oxidation state of the inorganic magnetite. Figure 7 shows the XRD pattern of CS-EDTA-MET @Fe 3 O 4 ( 1 ). There are symmetrical reactions at 2θ of 30.14°, 35.50°, 43.13°, 53.66°, 57.21°, and 62.71° which are characteristic of the CS-EDTA-MET @Fe 3 O 4 ( 1 ) structure according to the standard XRD patterns of chitosan (JCPDS card no. 00-039-1894), DL-methionine (JCPDS card no. 00-005-0311) EDTA (JCPDS card no. 00-033-1672), and Fe 3 O 4 (JCPDS card no. 01-076-0956). As can be seen, the results obtained from the XRD pattern of CS-EDTA-MET @Fe 3 O 4 ( 1 ). confirms the successful preparation of the desired nanomaterial. The VSM analysis has performed at room temperature by applying a magnetic field − 1000 to + 1000 oersted to measure the magnetic properties of the CS-EDTA-MET @Fe 3 O 4 ( 1 ) nanocatalyst. As can be seen in Fig. 8 , the phenomenon of hysteresis was not observed, which shows no residual loop, and this feature demonstrates that no accumulation occurs in the presence of a magnetic field. Moreover, the (S) curve for CS-EDTA-MET @Fe 3 O 4 ( 1 ) nanocatalyst confirms excellent paramagnetic behaviour without any hindrance or reluctance. In fact, the maximum magnetic saturation (Ms) is 18.57 emu/g. and this magnetic property of the CS-EDTA-MET @-Fe 3 O 4 ( 1 ) nanocatalyst is enough to be easily separated from the reaction mixture by an external magnet. Optimization of conditions for the synthesis of imidazole derivatives in the presence of CS-EDTA-MET@Fe 3 O 4 organocatalyst ( 1 ). In this section, the efficacy of CS-EDTA-MET@Fe 3 O 4 nanomaterial ( 1 ) in the model reaction for the synthesis of 2,4,5-trisubstituted imidazole derivatives were explored. Therefore, different parameters including solvent, catalyst loading, temperature, and reaction time were investigated to determine the optimal reaction conditions (Table 1 ). The model reaction was examined by using benzoin ( 2 , 1.0 mmol),4-chlorobenzaldehyde ( 3a , 1.0 mmol), and ammonium acetate ( 4 , 3.0 mmol) in the presence of CS-EDTA-MET@Fe 3 O 4 nanomaterial ( 1 ) for the synthesis of imidazole derivatives in various conditions. The results are summarized in Table 1 . The amount of the catalyst 1 plays an essential role in the model reaction. Indeed, the reaction in the absence of the CS-EDTA-MET@Fe 3 O 4 affords a poor yield of the desired 2-(4-chlorophenyl)-4,5-diphenyl-1 H -imidazole ( 5a ) after 360 min under reflux conditions ( entry 1 , Table 1 ). Moreover, the effect of other solvents including solvent-free conditions, H 2 O, MeOH, MeCN and EtOAc were also studied on the progress of the model reaction under same catalyst loading (entries 2–9). The highest yield of the desired product 5a was obtained by using 10 mg of catalyst loading 1 in EtOH at 60 o C ( entry 12 , Table 1 ). Consequently, among all the screened solvents EtOH was selected as the optimal solvent in the next experiments. The effect of lower catalyst loadings than 10 mg in different conditions were further studied ( entries 2–12 ). Moderate yields of the desired product 5a were obtained in all studied cases. The progress of the model reaction to afford the desired product 5a in EtOH were investigated in the presence of catalyst precursors as well to show their synergistic effects on the catalytic activity (Table 1 , entries 14–18 ). Based on the obtained results, the best conditions for this transformation is mentioned in entry 13 . The optimized reaction conditions (10 mg of CS-EDTA-MET@Fe 3 O 4 catalyst loading 1 , EtOH at 60 o C) were developed to other aromatic carbocyclic aldehydes 3b-k . The results are summarized in Table 2 . The studied aldehydes well survived under the optimized conditions to afford their corresponding 2,4,5-trisubstituted imidazole derivatives 3b-k in high to excellent yields. By adjusting the same reaction conditions for the four-component synthesis of imidazole derivatives, the fascinating results for 1,2,4,5-trisubstituted imidazole derivatives 7a-u were obtained which are mentioned in Table 3 . In this section of our study, a wide range of 1,2,4,5-trisubstituted imidazole derivatives were prepared by altering both aromatic carbocyclic aldehydes 3 as well as primary amine source as one of the reaction component. In general, aromatic aldehydes bearing electron withdrawing groups such as Cl, Br and NO 2 afford their corresponding imidazole derivatives 5 or 7 at higher yields compared to those containing electron releasing substituents such as Me, OH, OMe and NMe 2 substituents. The most plausible mechanisms for the synthesis of tri- and tetra-substituted imidazoles 5 or 7 catalyzed by the CS-EDTA-MET@Fe 3 O 4 nanomaterial ( 1 ) have been illustrated in (Fig. 9 ) . Indeed, the carbonyl groups of aldehydes 3 is activated by interaction with the Lewis acidic centers including Fe ions as well as hydrogen donors of catalyst ( 1 ). Then, nucleophiles including ammonia ( 4 ) and amines 6 can be added to the activated carbonyl group of aldehydes 3 to create the corresponding imine I and aminal II intermediates, respectively. After that, the aminal intermediate II reacts with the activated carbonyl group of benzoin ( 2 ) to afford cyclic intermediate III . This intermediate is formed by losing one molecules of water through simple imine condensation and subsequent air oxidation. Desired imidazole derivatives 5 or 7 are finally produced after a [1,5-H] shift in the structure of intermediate IV and liberates the catalyst ( 1 ) to start a new cycle of its catalytic activity. 100,136,148 One of the merits of heterogeneous nanomagnetic catalytic systems is their easy separation from the reaction mixture by means of an external magnet bar and subsequent reusing in the next designated catalytic-promoted transformations, which make them appropriate candidates for further applications in the relevant industrial process. In this part of our study, the reusability of CS-EDTA-MET@Fe 3 O 4 nanocatalyst ( 1 ) was investigated in the model reaction for further five runs. After completion of the reaction in each run, the nanocatalyst 1 was separated from the reaction mixture by using an external magnet and washed with EtOH. Then, it was dried in an oven at 70°C for 1 h. The recycled catalyst 1 was utilized for more five consecutive runs in the model reaction. The results are summarized in Fig. 10 . To our delight, the catalytic activity of the novel heterogeneous catalyst did not change significantly after six consecutive runs and only a little loss in the final yields was observed. Table 4 compares the efficiency of CS-EDTA-MET@Fe 3 O 4 organocatalyst ( 1 ) with other catalysts for the synthesis of imidazole derivatives 5a . For this comparison, several parameters, e.g., the reaction time, temperature, and the reaction yield, were taken into account. It can be implied that CS-EDTA-MET@Fe 3 O 4 heterogeneous catalyst ( 1 ) showed better performance than previously reported catalytic systems for the synthesis of imidazole derivatives. Table 4 Comparative results of the activity of different catalysts for the synthesis of 5a Entry Catalyst Catalyst loading Reaction conditions Time (min) 1 3-Picolinic acid 70 12 mg EtOH/80°C 120 2 PANI-FeCl 3 149 200 mg CH 3 CN/ Reflux 1440 3 PMAMOSa 100 15 mg EtOH/ Reflux 45 4 Nano- TiCl 4 .SiO 2 150 100 mg Solvent-free/ 130°C 30 5 K 5 CoW 12 O 40 ·3H 2 O 151 32 Solvent-free/140°C 180 6 Sulfonic acid functionalized silica 152 20 mg Solvent-free/140°C 100 7 CS-EDTA-MET@Fe 3 O 4 10 mg EtOH/ 60°C 45 Conclusions In summary, we have developed an effective and practical procedure for the synthesis of both tri- and tetra-substituted imidazole derivatives in the presence of DL-methionine grafted to chitosan by EDTA linker (CS-EDTA-MET@Fe 3 O 4 ) nanomaterial, as a heterogeneous magnetic organocatalyst, via the one-pot three and/or four-component condensation of benzoin, aromatic aldehydes, and amine sources. A wide range of desired products were smoothly prepared in high to excellent yields under low catalyst loading of CS-EDTA-MET@Fe 3 O 4 nanocatalyst and green conditions. The advantages of this method include appropriate catalytic activity, easy separation and reusability of the catalyst, high to excellent yield of products, use of green solvent, and mild reaction conditions. Moreover, this magnetic organocatalyst was recovered and reused at least five times without significant decrease in its activity. Additionally, the use of chitosan biopolymer in a modified form provides advantages in terms of the use of renewable feedstock as well as low toxic and biodegradable material in design and application of nano-ordered heterogeneous organocatalytic systems. Experimental section Reagents and Instruments All the materials of this research as well as the reagents were purchased from Merck and Aldrich and were used in the processes without further purification, except for benzaldehyde, which was used as a freshly distilled sample. DL-methionine (MW = 149.21 g.mol − 1 ) was purchased from an approved local supplier. Chitosan (CS, degree of deacetylation = 82 ± 2%, MW = 100–300 kDa) was Purchased from Acros Organics. Characterization of the CS-EDTA-MET@Fe 3 O 4 ( 1 ) was carried out using FESEM TESCAN-MIRA3, EDX Numerix DXP-X10P and TGA Bahr Company STA 504. FT-IR spectra were recorded as KBr pellets on a Perkin Elmer, 1720-X model (USA) spectrometer. 1 H NMR spectra (500 MHz) were obtained using Bruker DRX-500 Avance spectrometer in CDCl3 or DMSO‑d6, as solvent, at ambient temperature. To monitor the reactions progress, analytical thin layer chromatography (TLC) was performed using Merck 60 F-254 Al 0.2 mm silica gel plates. All yields refer to the isolated products. All the products are known compounds and were identified by comparison of their physical, spectroscopic and analytical data with the authentic samples. All products were characterized by spectroscopic methods (FTIR and 1 HNMR spectra) as well as measurement of melting points. Preparation of the catalyst CS-EDTA-MET@FeO nanomaterial (1) The procedure for preparation of the catalytic system is illustrated in Fig . S1 . General procedure for preparation of EDTA dianhydride (EDTADA) EDTA (10.0 g, 34 mmol), pyridine (16 mL), and acetic anhydride (14 mL) were charged into a 100 mL round bottom flask equipped with a condenser and a magnetic stirrer. The reaction was mixed and stirred at 65–70°C for 24 h under an Ar atmosphere. After completion of the reaction, the suspension was filtered and the crude product was washed carefully with acetic anhydride and dry diethyl ether under a stream of Ar to afford a white powder. The final product was dried by a rotary evaporator under vacuum at 40–50°C until getting fine and dry white powder (yield 90–92%, mp: 189–191 o C ( Scheme 3 ). 153 Preparation of the DL-methionine-EDTA monoanhydride (MET-MAEDTA) EDTADA (0.256 g, 1.0 mmol) was charged into a 25 mL two-neck round-bottom flask equipped with a reflux condenser and a magnet bar. Then, 3 ml of dry toluene was added under an Ar atmosphere. In addition, exactly one equivalent of DL-methionine (0.149 g, 1.0 mmol in 6.0 mL of toluene) was gradually added over 60 min. to control the selective reaction with one side of EDTADA. After that, the mixture was refluxed under constant stirring and Ar atmosphere for 18 h. Finally, the desired intermediate ( I ) was filtered and dried under vacuum at 60°C by using a rotary evaporator to afford a creamy white powder (0.394 g, Yield = 92.6%). 21,30 Preparation of DL-methionine-ETDA grafted on chitosan (CS-EDTA-MET) Intermediate I (0.16 g) and (chitosan, 0.32g) were charged into a 25 mL double-neck round-bottom flask containing dry toluene (10 mL). Then, the obtained mixture was stirred and heated at 60–70°C under an Ar atmosphere for 18 h. After completion of the reaction, the temperature cooled down to r.t. and the suspension was filtered and dried in a vacuum oven to afford (0.45 g, 93.75%) of the desired intermediate ( II ). Preparation of the CS-EDTA-MET@Fe 3 O 4 catalyst ( 1 ) 0.127 g of obtained CS-EDTA-MET was charged into a 250 mL two-neck round-bottom flask containing 10 mL water and heat to 70°C, then a mixture of (FeCl 2 :4H 2 O, 0.11 g and FeCl 3 :6H 2 O, 0.22 g) was added to the flask under inert Ar atmosphere followed by heating at 75°C for 10 min. After that, (NH 3 25%, 5 mL) was added dropwise under vigorous mixing and Ar atmosphere. The mixture colour turns black immediately. The suspension was mixed for more 2 h under mentioned conditions. The product was washed several times with 25 mL of deionized water to reach the pH range of 5–6. Finally the product was washed with EtOH and dried at 70°C to get 0.20 g of the magnetic catalyst ( 1 ) ( Fig . S1) . General Procedure for the Synthesis of tri- and tetra-substituted imidazole derivatives 5 or 7 in the presence of CS-EDTA-MET@Fe 3 O 4 ( 1 ) In a 10 mL flask, benzoin ( 2 , 1.0 mmol, 0.21 g), aldehyde ( 3 , 1.0 mmol, 0.14 g), and ammonium acetate ( 4 , 3.0 mmol, 0.23g) or/and amine (6, 1.0 mmol, 0.93 g) along with 0.01 g of CS-EDTA-MET@Fe3O4 ( 1 ) were added to EtOH 96% (5 mL). The obtained mixture was heated at 60°C for appropriate time mentioned in Table 2 , 3 . The progress of the reaction was monitored by thin layer chromatography (TLC) with EtOAc and n-hexane (3:1 V/V). After the completion of reaction, 5.0 mL of EtOH was added to the reaction mixture and heated to make a clear solution. After that, it was filtered off to separate the CS-EDTA-MET@Fe 3 O 4 ( 1 ) by using an external magnet. The filtrate was cooled and allowed to give pure product 5 or 7 by the crystallization method in the refrigerator. The crystals were collected by vacuum filtration, washed with EtOH and dried at 70°C for 1 h. Selected spectral data 4,5Diphenyl-2( p tolyl)-1 H imidazole ( 5e ) White solid; Yield 92%, mp 230–232°C (Lit. mp 232–234°C); 1 H NMR (400 MHz, CDCl 3 ): δ 2.42 (s, 3H, Me), 7.28–7.37 (m, 8H, Ar), 7.56 (d, J = 7.2 Hz, 4H, Ar), 7.82 (d, J = 8.4 Hz, 2H, Ar). 2(4Methoxyphenyl)-4,5diphenyl-1 H imidazole ( 5f ) White solid; Yield 93%, mp 226–229°C (Lit. mp 228–230°C); 1 H NMR (400 MHz, CDCl 3 ): δ 3.88 (s, 3H,OMe), 6.99 (d, J = 8.4 Hz, 2H, Ar), 7.30–7.77 (m, 10H, Ar), 7.86 (d, J = 8.8 Hz, 2H, Ar), 9.47 (brs, 1H, NH). 2-(3-Nitrophenyl)-1,4,5-triphenyl-1 H -imidazole ( 7b ) Mp: 249–251°C; Yellow solid; FTIR (KBr; cm − 1 ): 3427, 1525, 1344, 766, 697; 1 H NMR (500 MHz, DMSO- d 6 , ppm): δ 8.97 (d, J = 2.3 Hz, 1H), 8.53 (d, J = 7.9 Hz, 1H), 8.23 (d, J = 8.3 Hz, 1H), 8.18–8.13 (m, 1H), 7.80 (td, J = 8.2, 1.7 Hz, 1H), 7.61–7.26 (m, 14H). N , N -Dimethyl-4-(1,4,5-triphenyl-1 H -imidazol-2-yl)aniline ( 7g ) Mp: 205–207°C; Brown solid; FTIR (KBr; cm-1): 3422, 2926, 2364, 1722, 1612, 1488, 1442, 1370, 816, 694; 1 H NMR (500 MHz, DMSO- d 6 , ppm): δ 7.60–7.50 (m, 1H), 7.46 (d, J = 8.0 Hz, 2H), 7.37–7.31 (m, 4H), 7.21 (m, 10H), 6.56 (d, J = 8.0 Hz, 2H), 2.86 (s, 6H). 2-(4-Methoxyphenyl)-4,5-diphenyl-1-( p -tolyl)-1 H -imidazole ( 7m ). Mp: 178–181°C; White solid; FTIR (KBr; cm − 1 ): 2922, 2376, 1606, 1514, 1438, 1368, 1022, 824, 776, 698, 526; 1 H NMR (500 MHz, DMSO- d 6 , ppm): δ 7.50–7.47 (m, 2H), 7.35–7.30 (m, 5H), 7.25–7.22 (m, 4H), 7.18–7.11 (m, 5H), 6.89–6.85 (m, 2H), 3.74 (s, 3H), 2.27 (s, 3H). 1-Benzyl-2-(4-methoxyphenyl)-4,5-diphenyl-1 H -imidazole ( 7t ) Mp: 156–159°C; White solid; FTIR (KBr; cm − 1 ): 3026, 2929, 2361, 1605, 1530, 1482, 1449; 1 H NMR (500 MHz, CDCl 3 , ppm): δ 7.60–7.57 (m, 3H), 7.35–7.14 (m, 12H), 6.92 (d, J = 8.8 Hz, 2H), 6.82 (dd, J = 7.7, 1.7 Hz, 2H), 5.09 (s, 2H), 3.86–3.78 (m, 3H). Declarations Data availability All data generated or analyzed during this study are included in this published article [and its supplementary information files]. Contributions Mohammad Dohendou : Methodology, Investigation, Formal analysis, Writing-original draft; Mohammad G. Dekamin : Conceptualization, Resources, Project planning, Supervision, Financial, Editing-Final draft; Zahra Dehnamaki : Investigation, Formal analysis, Writing-original draft; Danial Namaki : Investigation, Formal analysis, Writing-original draft; Suranjana V. Mayani : Editing-Final draft, Methodology, Formal analysis. Conflict of interest The authors declare that there are no conflicts of interest regarding the publication of this manuscript. Acknowledgments We are grateful for the financial support from The Research Council of Iran University of Science and Technology (IUST), Tehran, Iran (Grant No. 160/23372). We would also like to acknowledge the support of The Iran Nanotechnology Initiative Council (INIC), Iran. Suranjana V. Mayani would also like to acknowledge Marwadi University, Rajkot, Gujarat, India. References Rai, P. K. et al. Nanoparticle-plant interaction: Implications in energy, environment, and agriculture. Environment international 119 , 1-19 (2018). Villalba-Rodríguez, A. M. et al. Nanomaterial Constructs for Catalytic Applications in Biomedicine: Nanobiocatalysts and Nanozymes. Topics in Catalysis 66 , 707-722, doi:10.1007/s11244-022-01766-4 (2023). Zhu, L. et al. Tannic acid modified keratin/sodium alginate/carboxymethyl chitosan biocomposite hydrogels with good mechanical properties and swelling behavior. Scientific Reports 14 , 12864, doi:10.1038/s41598-024-63186-6 (2024). Al-Azmi, A. & Keshipour, S. Cross-linked chitosan aerogel modified with Pd(II)/phthalocyanine: Synthesis, characterization, and catalytic application. Scientific Reports 9 , 13849, doi:10.1038/s41598-019-50021-6 (2019). Ahmed, M. E., Mohamed, M. I., Ahmed, H. Y., Elaasser, M. M. & Kandile, N. G. Fabrication and characterization of unique sustain modified chitosan nanoparticles for biomedical applications. Scientific Reports 14 , 13869, doi:10.1038/s41598-024-64017-4 (2024). Franco, F., Rettenmaier, C., Jeon, H. S. & Roldan Cuenya, B. Transition metal-based catalysts for the electrochemical CO2 reduction: from atoms and molecules to nanostructured materials. Chemical Society Reviews 49 , 6884-6946, doi:10.1039/D0CS00835D (2020). Zheng, B. et al. Rare-Earth Doping in Nanostructured Inorganic Materials. Chemical Reviews 122 , 5519-5603, doi:10.1021/acs.chemrev.1c00644 (2022). Shang, X., Yang, X., Liu, G., Zhang, T. & Su, X. A molecular view of single-atom catalysis toward carbon dioxide conversion. Chemical Science 15 , 4631-4708, doi:10.1039/D3SC06863C (2024). Mohan, A., Jaison, A. & Lee, Y.-C. Emerging trends in mesoporous silica nanoparticle-based catalysts for CO2 utilization reactions. Inorganic Chemistry Frontiers 10 , 3171-3194, doi:10.1039/D3QI00378G (2023). Jagadeesan, D. Multifunctional nanocatalysts for tandem reactions: A leap toward sustainability. Applied Catalysis A: General 511 , 59-77, doi:https://doi.org/10.1016/j.apcata.2015.11.033 (2016). Qin, Z. Nanostructure Design of Catalysts: Latest Advances and Prospects. Nanomaterials (Basel) 13 , doi:10.3390/nano13131980 (2023). Dohendou, M., Pakzad, K., Nezafat, Z., Nasrollahzadeh, M. & Dekamin, M. G. Progresses in chitin, chitosan, starch, cellulose, pectin, alginate, gelatin and gum based (nano)catalysts for the Heck coupling reactions: A review. International Journal of Biological Macromolecules 192 , 771-819, doi:https://doi.org/10.1016/j.ijbiomac.2021.09.162 (2021). Mahadevan, R., Palanisamy, S. & Sakthivel, P. Role of nanoparticles as oxidation catalyst in the treatment of textile wastewater: Fundamentals and recent advances. Sustainable Chemistry for the Environment 4 , 100044, doi:https://doi.org/10.1016/j.scenv.2023.100044 (2023). Baig, N., Kammakakam, I. & Falath, W. Nanomaterials: a review of synthesis methods, properties, recent progress, and challenges. Materials Advances 2 , 1821-1871, doi:10.1039/D0MA00807A (2021). Shetty, A., Molahalli, V., Sharma, A. & Hegde, G. Biomass-Derived Carbon Materials in Heterogeneous Catalysis: A Step towards Sustainable Future. Catalysts 13 (2023). Qiu, M., Zhan, S., Yu, H., Zhu, D. & Wang, S. Facile preparation of ordered mesoporous MnCo2O4 for low-temperature selective catalytic reduction of NO with NH3. Nanoscale 7 , 2568-2577, doi:10.1039/C4NR06451H (2015). Sharma, N., Ojha, H., Bharadwaj, A., Pathak, D. P. & Sharma, R. K. Preparation and catalytic applications of nanomaterials: a review. RSC Advances 5 , 53381-53403, doi:10.1039/C5RA06778B (2015). Chng, L. L., Erathodiyil, N. & Ying, J. Y. Nanostructured Catalysts for Organic Transformations. Accounts of Chemical Research 46 , 1825-1837, doi:10.1021/ar300197s (2013). Zhang, Y. et al. Nanostructured single-atom catalysts derived from natural building blocks. EES Catalysis 2 , 475-506, doi:10.1039/D3EY00265A (2024). Karami, S., Dekamin, M. G., Valiey, E. & Shakib, P. DABA MNPs: A new and efficient magnetic bifunctional nanocatalyst for the green synthesis of biologically active pyrano [2, 3-c] pyrazole and benzylpyrazolyl coumarin derivatives. New Journal of Chemistry 44 , 13952-13961 (2020). Rostami, N., Dekamin, M. G. & Valiey, E. Chitosan-EDTA-Cellulose bio-based network: A recyclable multifunctional organocatalyst for green and expeditious synthesis of Hantzsch esters. Carbohydrate Polymer Technologies and Applications 5 , 100279, doi:https://doi.org/10.1016/j.carpta.2022.100279 (2023). Valiey, E., Dekamin, M. G. & Alirezvani, Z. Melamine-modified chitosan materials: An efficient and recyclable bifunctional organocatalyst for green synthesis of densely functionalized bioactive dihydropyrano[2,3-c]pyrazole and benzylpyrazolyl coumarin derivatives. International Journal of Biological Macromolecules 129 , 407-421, doi:https://doi.org/10.1016/j.ijbiomac.2019.01.027 (2019). Sourkouhi, R. P., Dekamin, M. G., Valiey, E. & Dohendou, M. Magnetic decorated 5-sulfosalicylic acid grafted to chitosan: A solid acid organocatalyst for green synthesis of quinazoline derivatives. Carbohydrate Polymer Technologies and Applications 7 , 100420, doi:https://doi.org/10.1016/j.carpta.2023.100420 (2024). Ilkhanizadeh, S., Khalafy, J. & Dekamin, M. G. Sodium alginate: A biopolymeric catalyst for the synthesis of novel and known polysubstituted pyrano[3,2-c]chromenes. International Journal of Biological Macromolecules 140 , 605-613, doi:https://doi.org/10.1016/j.ijbiomac.2019.08.154 (2019). Dekamin, M. G. et al. Sodium alginate: An efficient biopolymeric catalyst for green synthesis of 2-amino-4H-pyran derivatives. International Journal of Biological Macromolecules 87 , 172-179, doi:https://doi.org/10.1016/j.ijbiomac.2016.01.080 (2016). Hong, M. et al. One-pot cascade production of 2,5-diformylfuran from glucose over catalysts from renewable resources. Catalysis Science & Technology 13 , 1335-1344, doi:10.1039/D2CY02017C (2023). Rostami, N., Dekamin, M. G., Valiey, E. & Fanimoghadam, H. Chitosan-EDTA-Cellulose network as a green, recyclable and multifunctional biopolymeric organocatalyst for the one-pot synthesis of 2-amino-4H-pyran derivatives. Scientific Reports 12 , 8642, doi:10.1038/s41598-022-10774-z (2022). Dekamin, M. G., Azimoshan, M. & Ramezani, L. Chitosan: a highly efficient renewable and recoverable bio-polymer catalyst for the expeditious synthesis of α-amino nitriles and imines under mild conditions. Green Chemistry 15 , 811-820, doi:10.1039/C3GC36901C (2013). Dohendou, M., Dekamin, M. G. & Namaki, D. Pd@l-asparagine–EDTA–chitosan: a highly effective and reusable bio-based and biodegradable catalyst for the Heck cross-coupling reaction under mild conditions. Nanoscale Advances 5 , 2621-2638, doi:10.1039/D3NA00058C (2023). Dohendou, M., Dekamin, M. G. & Namaki, D. Supramolecular Pd@methioine-EDTA-chitosan nanocomposite: an effective and recyclable bio-based and eco-friendly catalyst for the green Heck cross-coupling reaction under mild conditions. Nanoscale Advances , doi:10.1039/D3NA00157A (2023). Dekamin, M. G. et al. Alginic acid: A mild and renewable bifunctional heterogeneous biopolymeric organocatalyst for efficient and facile synthesis of polyhydroquinolines. Int J Biol Macromol 108 , 1273-1280, doi:10.1016/j.ijbiomac.2017.11.050 (2018). Alirezvani, Z., Dekamin, M. G., Davoodi, F. & Valiey, E. Melamine-Functionalized Chitosan: A New Bio-Based Reusable Bifunctional Organocatalyst for the Synthesis of Cyanocinnamonitrile Intermediates and Densely Functionalized Nicotinonitrile Derivatives. ChemistrySelect 3 , 10450-10463, doi:https://doi.org/10.1002/slct.201802010 (2018). Cioc, R. C., Ruijter, E. & Orru, R. V. Multicomponent reactions: advanced tools for sustainable organic synthesis. Green Chemistry 16 , 2958-2975 (2014). Dekamin, M. G. et al. Alginic acid: a highly efficient renewable and heterogeneous biopolymeric catalyst for one-pot synthesis of the Hantzsch 1, 4-dihydropyridines. RSC Advances 4 , 56658-56664 (2014). Dekamin, M. G., Kazemi, E., Karimi, Z., Mohammadalipoor, M. & Naimi-Jamal, M. R. Chitosan: An efficient biomacromolecule support for synergic catalyzing of Hantzsch esters by CuSO4. International Journal of Biological Macromolecules 93 , 767-774, doi:https://doi.org/10.1016/j.ijbiomac.2016.09.012 (2016). Dekamin, M. G. et al. Alginic acid: A mild and renewable bifunctional heterogeneous biopolymeric organocatalyst for efficient and facile synthesis of polyhydroquinolines. International Journal of Biological Macromolecules 108 , 1273-1280, doi:https://doi.org/10.1016/j.ijbiomac.2017.11.050 (2018). John, S. E., Gulati, S. & Shankaraiah, N. Recent advances in multi-component reactions and their mechanistic insights: a triennium review. Organic Chemistry Frontiers 8 , 4237-4287, doi:10.1039/D0QO01480J (2021). Safapoor, S., Dekamin, M. G., Akbari, A. & Naimi-Jamal, M. R. Synthesis of (E)-2-(1H-tetrazole-5-yl)-3-phenylacrylenenitrile derivatives catalyzed by new ZnO nanoparticles embedded in a thermally stable magnetic periodic mesoporous organosilica under green conditions. Scientific Reports 12 , 10723, doi:10.1038/s41598-022-13011-9 (2022). Rostami, N., Dekamin, M. G., Valiey, E. & FaniMoghadam, H. l-Asparagine–EDTA–amide silica-coated MNPs: a highly efficient and nano-ordered multifunctional core–shell organocatalyst for green synthesis of 3, 4-dihydropyrimidin-2 (1 H)-one compounds. RSC advances 12 , 21742-21759 (2022). Shakib, P., Dekamin, M. G., Valiey, E., Karami, S. & Dohendou, M. Ultrasound-Promoted preparation and application of novel bifunctional core/shell Fe3O4@SiO2@PTS-APG as a robust catalyst in the expeditious synthesis of Hantzsch esters. Scientific Reports 13 , 8016, doi:10.1038/s41598-023-33990-7 (2023). Ishani, M., Dekamin, M. G. & Alirezvani, Z. Superparamagnetic silica core-shell hybrid attached to graphene oxide as a promising recoverable catalyst for expeditious synthesis of TMS-protected cyanohydrins. Journal of Colloid and Interface Science 521 , 232-241, doi:https://doi.org/10.1016/j.jcis.2018.02.060 (2018). Fathi, M., Naimi-Jamal, M. R., Dekamin, M. G., Panahi, L. & Demchuk, O. M. A straightforward, environmentally beneficial synthesis of spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-2′,10,12-triones mediated by a nano-ordered reusable catalyst. Scientific Reports 11 , 4820, doi:10.1038/s41598-021-84209-6 (2021). Strecker, A. Ueber die künstliche Bildung der Milchsäure und einen neuen, dem Glycocoll homologen Körper. Justus Liebigs Annalen der Chemie 75 , 27-45 (1850). Hantzsch, A. Ueber die synthese pyridinartiger verbindungen aus acetessigäther und aldehydammoniak. Justus Liebigs Annalen der Chemie 215 , 1-82 (1882). Sam, M., Dekamin, M. G. & Alirezvani, Z. Dendrons containing boric acid and 1,3,5-tris(2-hydroxyethyl)isocyanurate covalently attached to silica-coated magnetite for the expeditious synthesis of Hantzsch esters. Scientific Reports 11 , 2399, doi:10.1038/s41598-020-80884-z (2021). Biginelli, P. & Gazz, P. Synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones. Gazz. Chim. Ital 23 , 360-416 (1893). Heravi, M. & Zadsirjan, V. in Recent Advances in Applications of Name Reactions in Multicomponent Reactions (eds Majid Heravi & Vahideh Zadsirjan) 139-268 (Elsevier, 2020). Yaghoubi, A. & Dekamin, M. G. Green and Facile Synthesis of 4H-Pyran Scaffold Catalyzed by Pure Nano-Ordered Periodic Mesoporous Organosilica with Isocyanurate Framework (PMO-ICS). ChemistrySelect 2 , 9236-9243, doi:https://doi.org/10.1002/slct.201700717 (2017). Bondarian, S., Dekamin, M. G., Valiey, E. & Naimi-Jamal, M. R. Supramolecular Cu(ii) nanoparticles supported on a functionalized chitosan containing urea and thiourea bridges as a recoverable nanocatalyst for efficient synthesis of 1H-tetrazoles. RSC Advances 13 , 27088-27105, doi:10.1039/D3RA01989F (2023). Nikooei, N., Dekamin, M. G. & Valiey, E. Benzene-1, 3, 5-tricarboxylic acid-functionalized MCM-41 as a novel and recoverable hybrid catalyst for expeditious and efficient synthesis of 2, 3-dihydroquinazolin-4 (1 H)-ones via one-pot three-component reaction. Research on Chemical Intermediates 46 , 3891-3909 (2020). Yaghoubi, A., Dekamin, M. G. & Karimi, B. Propylsulfonic Acid-Anchored Isocyanurate-Based Periodic Mesoporous Organosilica (PMO-ICS-PrSO3H): A Highly Efficient and Recoverable Nanoporous Catalyst for the One-Pot Synthesis of Substituted Polyhydroquinolines. Catalysis Letters 147 , 2656-2663, doi:10.1007/s10562-017-2159-5 (2017). Alinasab Amiri, A., Javanshir, S., Dolatkhah, Z. & Dekamin, M. G. SO3H-functionalized mesoporous silica materials as solid acid catalyst for facile and solvent-free synthesis of 2H-indazolo[2,1-b]phthalazine-1,6,11-trione derivatives. New Journal of Chemistry 39 , 9665-9671, doi:10.1039/C5NJ01733E (2015). Dekamin, M. G. & Eslami, M. Highly efficient organocatalytic synthesis of diverse and densely functionalized 2-amino-3-cyano-4H-pyrans under mechanochemical ball milling. Green Chemistry 16 , 4914-4921, doi:10.1039/C4GC00411F (2014). Machado, I. V., Dos Santos, J. R., Januario, M. A. & Corrêa, A. G. Greener organic synthetic methods: Sonochemistry and heterogeneous catalysis promoted multicomponent reactions. Ultrasonics Sonochemistry 78 , 105704 (2021). Brandão, P., Marques, C. S., Carreiro, E. P., Pineiro, M. & Burke, A. J. Engaging isatins in multicomponent reactions (MCRs)–easy access to structural diversity. The Chemical Record 21 , 924-1037 (2021). Rimaz, M., Mousavi, H., Ozzar, L. & Khalili, B. Facile, capable, atom-economical one-pot multicomponent strategy for the direct regioselective synthesis of novel isoxazolo [5, 4-d] pyrimidines. Research on Chemical Intermediates 45 , 2673-2694 (2019). Neochoritis, C. G., Zhao, T. & Dömling, A. Tetrazoles via multicomponent reactions. Chemical reviews 119 , 1970-2042 (2019). Sunderhaus, J. D., Dockendorff, C. & Martin, S. F. Applications of multicomponent reactions for the synthesis of diverse heterocyclic scaffolds. Organic letters 9 , 4223-4226 (2007). Cores, Á., Clerigué, J., Orocio-Rodríguez, E. & Menéndez, J. C. Multicomponent reactions for the synthesis of active pharmaceutical ingredients. Pharmaceuticals 15 , 1009 (2022). Weber, L. The application of multi-component reactions in drug discovery. Current Medicinal Chemistry 9 , 2085-2093 (2002). Ruijter, E. & Orru, R. V. Multicomponent reactions–opportunities for the pharmaceutical industry. Drug Discovery Today: Technologies 10 , e15-e20 (2013). Mohlala, R. L. & Coyanis, E. M. The vital use of isocyanide-based multicomponent reactions (MCR) in chemical synthesis. Physical Sciences Reviews (2023). Hossein Nia, R., Taati, Z. & Mamaghani, M. Multi-Component Synthesis of Indole-Substituted Heterocycles–A Review. Polycyclic Aromatic Compounds , 1-36 (2023). Alizadeh, M. H., Pooresmaeil, M. & Namazi, H. Carboxymethyl cellulose@multi wall carbon nanotubes functionalized with Ugi reaction as a new curcumin carrier. International Journal of Biological Macromolecules 234 , 123778, doi:https://doi.org/10.1016/j.ijbiomac.2023.123778 (2023). Orru, R. V. & Ruijter, E. Synthesis of heterocycles via multicomponent reactions II . Vol. 2 (Springer Science & Business Media, 2010). Zhu, J. & Bienaymé, H. Multicomponent reactions . (John Wiley & Sons, 2006). Ramón, D. J. & Yus, M. Asymmetric multicomponent reactions (AMCRs): the new frontier. Angewandte Chemie International Edition 44 , 1602-1634 (2005). Keivanloo, A., Bakherad, M., Imanifar, E. & Mirzaee, M. Boehmite nanoparticles, an efficient green catalyst for the multi-component synthesis of highly substituted imidazoles. Applied Catalysis A: General 467 , 291-300 (2013). Khazaei, A., Moosavi‐Zare, A. R., Gholami, F. & Khakyzadeh, V. Preparation of 1, 2, 4, 5‐tetrasubstituted imidazoles over magnetic core–shell titanium dioxide nanoparticles. Applied Organometallic Chemistry 30 , 691-694 (2016). Al Munsur, A. Z., Roy, H. N. & Imon, M. K. Highly efficient and metal-free synthesis of tri-and tetrasubstituted imidazole catalyzed by 3-picolinic acid. Arabian Journal of Chemistry 13 , 8807-8814 (2020). Gabla, J. J., Mistry, S. R. & Maheria, K. C. An efficient green protocol for the synthesis of tetra-substituted imidazoles catalyzed by zeolite BEA: effect of surface acidity and polarity of zeolite. Catalysis Science & Technology 7 , 5154-5167 (2017). Nicolaou, K. C., Montagnon, T. & Snyder, S. A. Tandem reactions, cascade sequences, and biomimetic strategies in total synthesis. Chem Commun (Camb) , 551-564, doi:10.1039/b209440c (2003). Rotstein, B. H., Zaretsky, S., Rai, V. & Yudin, A. K. Small heterocycles in multicomponent reactions. Chemical reviews 114 , 8323-8359 (2014). de Graaff, C., Ruijter, E. & Orru, R. V. Recent developments in asymmetric multicomponent reactions. Chemical Society Reviews 41 , 3969-4009 (2012). Jiang, B., Rajale, T., Wever, W., Tu, S. J. & Li, G. Multicomponent reactions for the synthesis of heterocycles. Chemistry–An Asian Journal 5 , 2318-2335 (2010). Wang, X. B., He, L., Jian, T. Y. & Ye, S. Cyclic phosphoric acid catalyzed one-pot, four-component synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles. Chinese Chemical Letters 23 , 13-16 (2012). Silver, M. A. & Albrecht-Schmitt, T. E. Evaluation of f-element borate chemistry. Coordination Chemistry Reviews 323 , 36-51 (2016). Lv, L. et al. Silver‐Catalyzed [3+ 1+ 1] Annulation of Nitrones with Isocyanoacetates as an Approach to 1, 4, 5‐Trisubstituted Imidazoles. European Journal of Organic Chemistry 2021 , 964-968 (2021). Balalaie, S. & Arabanian, A. One-pot synthesis of tetrasubstituted imidazoles catalyzed by zeolite HY and silica gel under microwave irradiation. Green Chemistry 2 , 274-276 (2000). Perrine, D. M., Ross, J. T., Nervi, S. J. & Zimmerman, R. H. A short, one-pot synthesis of bupropion (Zyban, Wellbutrin). Journal of Chemical Education 77 , 1479 (2000). Dai, B. et al. Iodine catalyzed one-pot multi-component reaction to CF3-containing spiro [indene-2, 3′-piperidine] derivatives. Journal of Fluorine Chemistry 133 , 127-133 (2012). Rahman, M., Bagdi, A. K., Kundu, D., Majee, A. & Hajra, A. Zwitterionic‐Type Molten Salt‐Catalyzed Multicomponent Reactions: One‐Pot Synthesis of Substituted Imidazoles Under Solvent‐Free Conditions. Journal of Heterocyclic Chemistry 49 , 1224-1228 (2012). Tavakoli, Z., Bagherneghad, M. & Niknam, K. Synthesis of 1, 2, 4, 5‐tetrasubstituted imidazoles using Sulfuric acid ([3‐(3‐Silicapropyl) sulfanyl] propyl] ester as a recyclable solid acid. Journal of Heterocyclic Chemistry 49 , 634-639 (2012). Wan, Y. et al. One‐Pot Synthesis of 1, 2, 4, 5‐Tetrasubstituted Imidazoles in Ionic Liquid. Journal of Heterocyclic Chemistry 51 , 713-718 (2014). Laufer, S. A., Zimmermann, W. & Ruff, K. J. Tetrasubstituted imidazole inhibitors of cytokine release: probing substituents in the N-1 position. Journal of medicinal chemistry 47 , 6311-6325 (2004). Heravi, M. M. et al. Solvent-free multicomponent reactions using the novel N-sulfonic acid modified poly (styrene-maleic anhydride) as a solid acid catalyst. Journal of Molecular Catalysis A: Chemical 392 , 173-180 (2014). Kidwai, M. et al. One-pot synthesis of highly substituted imidazoles using molecular iodine: A versatile catalyst. Journal of Molecular Catalysis A: Chemical 265 , 177-182 (2007). Shaabani, A. & Rahmati, A. Silica sulfuric acid as an efficient and recoverable catalyst for the synthesis of trisubstituted imidazoles. Journal of Molecular Catalysis A: Chemical 249 , 246-248 (2006). Teimouri, A. & Chermahini, A. N. An efficient and one-pot synthesis of 2, 4, 5-trisubstituted and 1, 2, 4, 5-tetrasubstituted imidazoles catalyzed via solid acid nano-catalyst. Journal of Molecular Catalysis A: Chemical 346 , 39-45 (2011). Shaterian, H. R. & Ranjbar, M. An environmental friendly approach for the synthesis of highly substituted imidazoles using Brønsted acidic ionic liquid, N-methyl-2-pyrrolidonium hydrogen sulfate, as reusable catalyst. Journal of Molecular Liquids 160 , 40-49 (2011). Wu, L., Jing, X., Zhu, H., Liu, Y. & Yan, C. One-pot synthesis of polysubstituted imidazoles from arylaldehydes in water catalyzed by NHC using microwave irradiation. Journal of the Chilean Chemical Society 57 , 1204-1207 (2012). Khodaei, M. M., Bahrami, K. & Kavianinia, I. p‐TSA catalyzed synthesis of 2, 4, 5‐triarylimidazoles from ammonium heptamolybdate tetrahydrate in TBAI. Journal of the Chinese Chemical Society 54 , 829-833 (2007). Sadeghi, B., Mirjalili, B., Bidaki, S. & Ghasemkhani, M. SbCl5. SiO2: an efficient alternative for one-pot synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles in solvent or under solvent-free condition. Journal of the Iranian Chemical Society 8 , 648-652 (2011). Tietze, L. F. & Modi, A. Multicomponent domino reactions for the synthesis of biologically active natural products and drugs. Med Res Rev 20 , 304-322, doi:10.1002/1098-1128(200007)20:43.0.co;2-8 (2000). Bahrami, K., Khodaei, M. M. & Nejati, A. One-pot synthesis of 1, 2, 4, 5-tetrasubstituted and 2, 4, 5-trisubstituted imidazoles by zinc oxide as efficient and reusable catalyst. Monatshefte für Chemie-Chemical Monthly 142 , 159-162 (2011). Das, B., Kashanna, J., Kumar, R. A. & Jangili, P. Synthesis of 2, 4, 5-trisubstituted and 1, 2, 4, 5-tetrasubstituted imidazoles in water using p-dodecylbenzenesulfonic acid as catalyst. Monatshefte für Chemie-Chemical Monthly 144 , 223-226 (2013). Heravi, M. M., Derikvand, F. & Haghighi, M. Highly efficient, four component, one-pot synthesis of tetrasubstituted imidazoles using a catalytic amount of FeCl3· 6H2O. Monatshefte für Chemie-Chemical Monthly 139 , 31-33 (2008). Patil, M. S., Khatri, C. K. & Chaturbhuj, G. U. Three-component, solvent-free synthesis of Betti base catalyzed by sulfated polyborate. Monatshefte für Chemie-Chemical Monthly 149 , 1453-1457 (2018). Wu, C. et al. In situ formation of H-bonding imidazole chains in break-junction experiments. Nanoscale 12 , 7914-7920 (2020). Valiey, E. & Dekamin, M. G. Pyromellitic diamide–diacid bridged mesoporous organosilica nanospheres with controllable morphologies: a novel PMO for the facile and expeditious synthesis of imidazole derivatives. Nanoscale Advances 4 , 294-308 (2022). Zarnegar, Z. & Safari, J. Catalytic activity of Cu nanoparticles supported on Fe 3 O 4–polyethylene glycol nanocomposites for the synthesis of substituted imidazoles. New Journal of Chemistry 38 , 4555-4565 (2014). Shabalin, D. A. & Camp, J. E. Recent advances in the synthesis of imidazoles. Org Biomol Chem 18 , 3950-3964, doi:10.1039/d0ob00350f (2020). Zhu, Y. et al. A Facile FeCl3/I2-Catalyzed Aerobic Oxidative Coupling Reaction: Synthesis of Tetrasubstituted Imidazoles from Amidines and Chalcones. Org Lett 17 , 3872-3875, doi:10.1021/acs.orglett.5b01854 (2015). Sparks, R. B. & Combs, A. P. Microwave-Assisted Synthesis of 2, 4, 5-Triaryl-imidazole; A Novel Thermally Induced N-Hydroxyimidazole N− O Bond Cleavage. Organic letters 6 , 2473-2475 (2004). Wolkenberg, S. E. et al. Efficient synthesis of imidazoles from aldehydes and 1, 2-diketones using microwave irradiation. Organic Letters 6 , 1453-1456 (2004). Maleki, B., Kahoo, G. E. & Tayebee, R. One-pot synthesis of polysubstituted imidazoles catalyzed by an ionic liquid. Organic Preparations and Procedures International 47 , 461-472 (2015). Zhang, F. et al. A practical and green approach towards synthesis of multisubstituted imidazoles using boric acid as efficient catalyst. Phosphorus, Sulfur, and Silicon and the Related Elements 191 , 786-789 (2016). Tietze, L. F. & Rackelmann, N. Domino reactions in the synthesis of heterocyclic natural products and analogs. Pure and Applied Chemistry 76 , 1967-1983, doi:doi:10.1351/pac200476111967 (2004). Esmaeilpour, M., Javidi, J., Dehghani, F. & Zahmatkesh, S. One-pot synthesis of multisubstituted imidazoles catalyzed by Dendrimer-PWAn nanoparticles under solvent-free conditions and ultrasonic irradiation. Research on Chemical Intermediates 43 , 163-185 (2017). FaniMoghadam, H., Dekamin, M. G. & Rostami, N. Para-Aminobenzoic acid grafted on silica-coated magnetic nanoparticles: a highly efficient and synergistic organocatalyst for on-water synthesis of 2, 3-dihydroquinazolin-4 (1H)-ones. Research on Chemical Intermediates 48 , 3061-3089 (2022). Hanoon, H., Kowsari, E., Abdouss, M., Ghasemi, M. & Zandi, H. Highly efficient and simple protocol for synthesis of 2, 4, 5-triarylimidazole derivatives from benzil using fluorinated graphene oxide as effective and reusable catalyst. Research on Chemical Intermediates 43 , 4023-4041 (2017). Saghanezhad, S. J., Sayahi, M. H., Imanifar, I., Mombeni, M. & Deris Hamood, S. Caffeine-H3PO4: a novel acidic catalyst for various one-pot multicomponent reactions. Research on Chemical Intermediates 43 , 6521-6536 (2017). Radinekiyan, F. et al. A magnetic cross-linked alginate-biobased nanocomposite with anticancer and hyperthermia activities. Carbohydrate Polymer Technologies and Applications 7 , 100481, doi:https://doi.org/10.1016/j.carpta.2024.100481 (2024). Choopani, L. et al. Fabrication of a magnetic nanocomposite based on natural hydrogel: Pectin, tragacanth gum, silk fibroin, and integrated graphitic carbon nitride for hyperthermia and biological features. Carbohydrate Polymer Technologies and Applications 7 , 100495, doi:https://doi.org/10.1016/j.carpta.2024.100495 (2024). Chen, L. et al. Polycarboxylate functionalized magnetic nanoparticles Fe3O4@SiO2@CS-COOH: Preparation, characterization, and immobilization of bovine serum albumin. International Journal of Biological Macromolecules 260 , 129617, doi:https://doi.org/10.1016/j.ijbiomac.2024.129617 (2024). Bahojb Noruzi, E. et al. Chemical and physical modification of graphene oxide nano-sheets using casein, Zn-Al layered double hydroxide, alginate hydrogel, and magnetic nanoparticles for biomedical applications. International Journal of Biological Macromolecules 269 , 132047, doi:https://doi.org/10.1016/j.ijbiomac.2024.132047 (2024). Karami, N. et al. Green synthesis of sustainable magnetic nanoparticles Fe3O4 and Fe3O4-chitosan derived from Prosopis farcta biomass extract and their performance in the sorption of lead(II). International Journal of Biological Macromolecules 254 , 127663, doi:https://doi.org/10.1016/j.ijbiomac.2023.127663 (2024). Mavvaji, M. & Akkoc, S. Recent advances in the application of heterogeneous catalysts for the synthesis of benzimidazole derivatives. Coordination Chemistry Reviews 505 , 215714, doi:https://doi.org/10.1016/j.ccr.2024.215714 (2024). Verma, S. K., Bhadauria, S. S. & Akhtar, S. Review of nondestructive testing methods for condition monitoring of concrete structures. Journal of construction engineering 2013 , 1-11 (2013). Thimmaraju, N. & Shamshuddin, S. M. Synthesis of 2, 4, 5-trisubstituted imidazoles, quinoxalines and 1, 5-benzodiazepines over an eco-friendly and highly efficient ZrO 2–Al 2 O 3 catalyst. RSC advances 6 , 60231-60243 (2016). Akbari, A., Dekamin, M. G., Yaghoubi, A. & Naimi-Jamal, M. R. Novel magnetic propylsulfonic acid-anchored isocyanurate-based periodic mesoporous organosilica (Iron oxide@PMO-ICS-PrSO3H) as a highly efficient and reusable nanoreactor for the sustainable synthesis of imidazopyrimidine derivatives. Scientific Reports 10 , 10646, doi:10.1038/s41598-020-67592-4 (2020). Rostamnia, S. & Doustkhah, E. Increased SBA-15-SO3H catalytic activity through hydrophilic/hydrophobic fluoroalkyl-chained alcohols (RFOH/SBA-15–Pr-SO3H). Synlett 26 , 1345-1347 (2015). Kumar, T. D. A., Yamini, N., Subrahmanyam, C. & Satyanarayana, K. Design and Optimization of Ecofriendly One-Pot Synthesis of 2, 4, 5-Triaryl-1 H-imidazoles by Three-Component Condensation Using Response Surface Methodology. Synthetic Communications 44 , 2256-2268 (2014). Davoodnia, A., Heravi, M. M., Safavi-Rad, Z. & Tavakoli-Hoseini, N. Green, one-pot, solvent-free synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles using a Brønsted acidic ionic liquid as novel and reusable catalyst. Synthetic Communications® 40 , 2588-2597 (2010). Padwa, A. & Bur, S. K. The domino way to heterocycles. Tetrahedron 63 , 5341 (2007). Samai, S., Nandi, G. C., Singh, P. & Singh, M. L-Proline: an efficient catalyst for the one-pot synthesis of 2, 4, 5-trisubstituted and 1, 2, 4, 5-tetrasubstituted imidazoles. Tetrahedron 65 , 10155-10161 (2009). Mukhopadhyay, C., Tapaswi, P. K. & Drew, M. G. Room temperature synthesis of tri-, tetrasubstituted imidazoles and bis-analogues by mercaptopropylsilica (MPS) in aqueous methanol: application to the synthesis of the drug trifenagrel. Tetrahedron Letters 51 , 3944-3950 (2010). Niknam, K., Deris, A., Naeimi, F. & Majleci, F. Synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles using silica-bonded propylpiperazine N-sulfamic acid as a recyclable solid acid catalyst. Tetrahedron letters 52 , 4642-4645 (2011). Patil, M. S., Palav, A. V., Khatri, C. K. & Chaturbhuj, G. U. Rapid, efficient and solvent-free synthesis of (un) symmetrical xanthenes catalyzed by recyclable sulfated polyborate. Tetrahedron Letters 58 , 2859-2864 (2017). Rekunge, D. S., Khatri, C. K. & Chaturbhuj, G. U. Sulfated polyborate-catalyzed efficient and expeditious synthesis of (un) symmetrical ureas and benzimidazolones. Tetrahedron Letters 58 , 4304-4307 (2017). Malihishoja, A., Dekamin, M. G. & Eslami, M. Magnetic polyborate nanoparticles as a green and efficient catalyst for one-pot four-component synthesis of highly substituted imidazole derivatives. RSC Advances 13 , 16584-16601, doi:10.1039/D3RA02262E (2023). Rossi, R. A., Gaetano; Casotti, Gianluca; Manzini, Chiara, Lessi, Marco. Catalytic Synthesis of 1,2,4,5-Tetrasubstituted 1H-Imidazole Derivatives: State of the Art. Advanced Synthesis & Catalysis 361 , 2737-2803, doi:10.1002/adsc.201801381 (2019). Sadeghi, B., Mirjalili, B. B. F. & Hashemi, M. M. BF3· SiO2: an efficient reagent system for the one-pot synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles. Tetrahedron Letters 49 , 2575-2577 (2008). Sivakumar, K., Kathirvel, A. & Lalitha, A. Simple and efficient method for the synthesis of highly substituted imidazoles using zeolite-supported reagents. Tetrahedron Letters 51 , 3018-3021 (2010). El hajri, F. et al. Investigation of catalytic performance of Bis [hydrazinium (1+)] hexafluoridosilicate: (N2H5)2SiF6 in synthesis of 2,4,5-triaryl-1H-imidazoles and 2,3-dihydroquinazolin-4 (1H)-ones under Green conditions. Inorganica Chimica Acta 536 , 120915, doi:https://doi.org/10.1016/j.ica.2022.120915 (2022). Fattahi, B. & Dekamin, M. G. Fe3O4/SiO2 decorated trimesic acid-melamine nanocomposite: a reusable supramolecular organocatalyst for efficient multicomponent synthesis of imidazole derivatives. Scientific Reports 13 , 401, doi:10.1038/s41598-023-27408-7 (2023). Samai, S., Nandi, G. C., Singh, P. & Singh, M. S. l-Proline: an efficient catalyst for the one-pot synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles. Tetrahedron 65 , 10155-10161, doi:https://doi.org/10.1016/j.tet.2009.10.019 (2009). Khazaei, A., Nik, H. A. A., Ranjbaran, A. & Moosavi-Zare, A. R. Synthesis, characterization and application of Ni 0.5 Zn 0.5 Fe 2 O 4 nanoparticles for the one pot synthesis of triaryl-1 H-imidazoles. RSC Advances 6 , 78881-78886 (2016). Eidi, E., Kassaee, M. Z. & Nasresfahani, Z. Synthesis of 2, 4, 5‐trisubstituted imidazoles over reusable CoFe2O4 nanoparticles: an efficient and green sonochemical process. Applied Organometallic Chemistry 30 , 561-565 (2016). Nguyen, T. T., Le, N.-P. T. & Tran, P. H. An efficient multicomponent synthesis of 2, 4, 5-trisubstituted and 1, 2, 4, 5-tetrasubstituted imidazoles catalyzed by a magnetic nanoparticle supported Lewis acidic deep eutectic solvent. RSC Advances 9 , 38148-38153 (2019). Goudarziafshar, H., Moosavi-Zare, A. R. & Jalilian, Z. Synthesis of 2, 4, 5-Tri substituted Imidazoles Using Nano-[Zn-2BSMP] Cl2 as a Schiff Base Complex and Catalyst. Organic Chemistry Research 6 , 69-81 (2020). Sparks, R. B. & Combs, A. P. Microwave-Assisted Synthesis of 2,4,5-Triaryl-imidazole; A Novel Thermally Induced N-Hydroxyimidazole N−O Bond Cleavage. Organic Letters 6 , 2473-2475, doi:10.1021/ol049124x (2004). Padwa, A. & Bur, S. K. The Domino Way to Heterocycles. Tetrahedron 63 , 5341-5378, doi:10.1016/j.tet.2007.03.158 (2007). Moosavi-Zare, A. R., Asgari, Z., Zare, A., Zolfigol, M. A. & Shekouhy, M. One pot synthesis of 1, 2, 4, 5-tetrasubstituted-imidazoles catalyzed by trityl chloride in neutral media. RSC advances 4 , 60636-60639 (2014). Al Munsur, A. Z., Roy, H. N. & Imon, M. K. Highly efficient and metal-free synthesis of tri- and tetrasubstituted imidazole catalyzed by 3-picolinic acid. Arabian Journal of Chemistry 13 , 8807-8814, doi:https://doi.org/10.1016/j.arabjc.2020.10.010 (2020). Dai, B. et al. Iodine catalyzed one-pot multi-component reaction to CF3-containing spiro[indene-2,3′-piperidine] derivatives. Journal of Fluorine Chemistry 133 , 127-133, doi:https://doi.org/10.1016/j.jfluchem.2011.09.006 (2012). Nicolaou, K. C., Montagnon, T. & Snyder, S. A. Tandem reactions, cascade sequences, and biomimetic strategies in total synthesis. Chemical Communications , 551-564, doi:10.1039/B209440C (2003). Zolfigol, M. A., Baghery, S., Moosavi-Zare, A. R. & Vahdat, S. M. Synthesis of 1,2,4,5-tetrasubstituted imidazoles using 2,6-dimethylpyridinium trinitromethanide {[2,6-DMPyH]C(NO2)3} as a novel nanostructured molten salt and green catalyst. RSC Advances 5 , 32933-32940, doi:10.1039/C5RA03241E (2015). Abdollahi-Alibeik, M. & Moosavifard, M. FeCl3-Doped Polyaniline Nanoparticles as Reusable Heterogeneous Catalyst for the Synthesis of 2-Substituted Benzimidazoles. Synthetic Communications 40 , 2686-2695, doi:10.1080/00397910903318658 (2010). Mirjalili, B. F., Bamoniri, A. H. & Zamani, L. One-pot synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles promoted by nano-TiCl4.SiO2. Scientia Iranica 19 , 565-568, doi:https://doi.org/10.1016/j.scient.2011.12.013 (2012). Nagarapu, L., Apuri, S. & Kantevari, S. Potassium dodecatugstocobaltate trihydrate (K5CoW12O40·3H2O): A mild and efficient reusable catalyst for the one-pot synthesis of 1,2,4,5-tetrasubstituted imidazoles under conventional heating and microwave irradiation. Journal of Molecular Catalysis A: Chemical 266 , 104-108, doi:https://doi.org/10.1016/j.molcata.2006.10.056 (2007). Mohammadi Ziarani, G., Dashtianeh, Z., Shakiba Nahad, M. & Badiei, A. One-pot synthesis of 1,2,4,5-tetra substituted imidazoles using sulfonic acid functionalized silica (SiO2-Pr-SO3H). Arabian Journal of Chemistry 8 , 692-697, doi:https://doi.org/10.1016/j.arabjc.2013.11.020 (2015). Arsalani, N. & Mousavi, S. Z. Synthesis and characterization of water-soluble and carboxy-functional polyester and polyamide based on ethylenediamine-tetraacetic acid and their metal complexes. (2003). Table 1 To 3 Table 1 to 3 are available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files ElectronicSupportingInformationFinalized.docx Table1to3.docx Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4619378","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":328393672,"identity":"44320bdb-a85a-470f-9427-20fc7ded5946","order_by":0,"name":"Mohammad Dohendou","email":"","orcid":"","institution":"Iran University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Mohammad","middleName":"","lastName":"Dohendou","suffix":""},{"id":328393673,"identity":"a7698c93-c122-4bed-aa93-cfa1c9c9254c","order_by":1,"name":"Mohammad G. 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scaffold\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4619378/v1/311e5134000a14466476c854.png"},{"id":60567957,"identity":"59c66010-738d-48d3-ab23-e67b328b2703","added_by":"auto","created_at":"2024-07-18 08:56:49","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":213613,"visible":true,"origin":"","legend":"\u003cp\u003eSynthesis of 2,3,4-trisubstituted and 1,2,3,4-tetrasubstituted imidazole derivatives catalyzed by CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (\u003cstrong\u003e1\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4619378/v1/cdfcc94f83fe4b0c9ea06c8c.png"},{"id":60567948,"identity":"edf7fbfc-f3dd-409b-be5d-e30d3eea214b","added_by":"auto","created_at":"2024-07-18 08:56:48","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":122658,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra of the commercial Chitosan (\u003cstrong\u003ea\u003c/strong\u003e), CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e, \u003cstrong\u003eb\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4619378/v1/ee7298a1fab789a39a6eb0bd.png"},{"id":60568519,"identity":"c0c082a7-e19d-4e3d-84c8-85c27fa17f2f","added_by":"auto","created_at":"2024-07-18 09:04:48","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":253499,"visible":true,"origin":"","legend":"\u003cp\u003eEDS spectra of the CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e organocatalyst 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6","display":"","copyAsset":false,"role":"figure","size":123043,"visible":true,"origin":"","legend":"\u003cp\u003eTGA (blue curve) and DTA (red curve) of the CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanomaterial (\u003cstrong\u003e1).\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-4619378/v1/e59702887198ed684b15fe24.png"},{"id":60567955,"identity":"c79553ad-c3ef-4861-89ca-6d9a74e423af","added_by":"auto","created_at":"2024-07-18 08:56:49","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":369695,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Wide-Angle XRD pattern of the CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4 \u003c/sub\u003enanomaterial (1) and (b) and its comparison with the X'pert highscore 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9","display":"","copyAsset":false,"role":"figure","size":1050473,"visible":true,"origin":"","legend":"\u003cp\u003eThe most plausible mechanism for the synthesis of tetra- and tri- substituted imidazole derivatives \u003cstrong\u003e5\u003c/strong\u003e or \u003cstrong\u003e7\u003c/strong\u003e in the presence of CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e organocatalyst (\u003cstrong\u003e1\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-4619378/v1/d5be0b1f5d30e374187793f9.png"},{"id":60567966,"identity":"024eb70d-7d7f-4b42-a39d-668da8499fd1","added_by":"auto","created_at":"2024-07-18 08:56:50","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":21368,"visible":true,"origin":"","legend":"\u003cp\u003eReusability of the CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e organocatalyst (1) in 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under green conditions","fulltext":[{"header":"Introduction","content":"\u003cp\u003eNanomaterials are being explored and utilized across various sectors such as biomedicine and nanomedicine, energy storage and transformation, environment remediation and water purification, catalysis, etc\u003csup\u003e1\u0026ndash;5\u003c/sup\u003e. In this context, nano-ordered catalytic systems have received great interest in recent years due to their high activity resulting from high surface to volume ratio and appropriate dispersion of active sites, shape-selectivity and quantum size effect as well as the ability to be recycled and reused repetitively to address the gap between the classic homogenous and bulk heterogeneous catalysts and making a bridge between these active research fields\u003csup\u003e4,6\u0026ndash;25\u003c/sup\u003e. This impact can be intensified when biopolymers and their modified forms, as the heterogeneous version of organocatalysts, come to play and add more advantages to the designed nano-ordered catalytic systems in terms of zero or low toxicity as well as their biodegradability after retirement\u003csup\u003e21,26\u0026ndash;32\u003c/sup\u003e. Furthermore, multifunctional nanocatalysts are very beneficial to promote multi-step reaction requiring same or different active sites in a single pot. All these criteria make the processes greener and more sustainable, especially for atom-/step economic multicomponent reactions (MCRs) \u003csup\u003e28,31,33\u0026ndash;36\u003c/sup\u003e. Nowadays, MCRs are effective tools and procedures to prepare complex scaffolds, which are important in the fine chemical industry including pharmaceutical, dyes and color industries, etc\u003csup\u003e37\u0026ndash;42\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe invention of MCRs goes back to middle of 19th century by pioneer scientists including Strecker\u003csup\u003e\u003cb\u003e28,43\u003c/b\u003e\u003c/sup\u003e, Hantzsch\u003csup\u003e44,45\u003c/sup\u003e, Biginelli\u003csup\u003e39,46\u003c/sup\u003e. MCRs are convergent reactions, in which more than two commercially accessible precursors have been mixed together to react and form important acyclic or heterocyclic products with high bond formation index (BFI) \u003csup\u003e47\u0026ndash;53\u003c/sup\u003e. In recent decades, MCRs have emerged as an interesting tool that allows the simple synthesis of complex molecules in one-pot synthesis, without separating and purifying intermediates; therefore, it leads to cost, time and energy reduction\u003csup\u003e54\u0026ndash;58\u003c/sup\u003e. However, MCRS generally requires homogenous or heterogeneous catalytic systems to afford high to excellent yields in shorter reaction times, which are important factors in designing of new processes in the pharmaceutical industry. Hence, (MCRs) in combination with nano-ordered catalysts have received significant interest for the synthesis of many pharmaceuticals or other fine chemicals in recent years\u003csup\u003e10\u0026ndash;14,59-64\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eDue to importance of MCRs in different fields of science including chemical and pharmaceutical sectors, the application of a novel, robust and convenient catalytic methods is demanded. Therefore, to cover the principles of GC in terms of less hazardous materials, inexpensive methods, effective and high yields protocols, a variety of catalytic systems have been considered recently\u003csup\u003e65\u0026ndash;74\u003c/sup\u003e. Among these, due to provide magnetic properties as support for different organic transformations as well as their proper surface area and nanomagnetic characteristics, magnetic nanoparticles have received scientific attention in different fields of catalytic systems including Bronsted acid/or base, traditional metal, organo- and enzymatic catalysis reactions. As a result, chemical stability, being specifically robust as well as availability with a naturally low toxicity and cost has made them efficient replacements to other known catalyst supports especially silica and alumina\u003csup\u003e20,31,33,34,75\u0026ndash;117\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eImidazole derivatives have occupied a unique position in the heterocyclic chemistry. They are \u003cem\u003eN\u003c/em\u003e-containing heterocyclic ring that possess versatile properties in the both chemical and pharmaceutical sectors\u003csup\u003e118\u003c/sup\u003e. The imidazole scaffold is existing in the several important natural products including purine, histamine, histidine, and nucleic acid. Having both polar and ionizable properties improves the pharmacokinetic characteristics and make imidazole heterocycles an important group that can cover an extensive spectrum of biologically active materials comprising antibacterial, anticancer, antitubercular, antifungal, analgesic, and anti-HIV compounds\u003csup\u003e27,38,45,119\u0026ndash;122\u003c/sup\u003e \u003cb\u003e(\u003c/b\u003eFig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u003cb\u003e)\u003c/b\u003e. Additionally, highly-substituted 1,3-dialkylimidazoles have shown high potential in the form of ionic liquids, as green solvents, or precursors of \u003cem\u003eN\u003c/em\u003e-heterocyclic carbens (NHCs). The NHCs are of interest as effective organocatlysts or ligands in coordination chemistry recently\u003csup\u003e123\u0026ndash;126\u003c/sup\u003e. Hence the advantages and vast applications of imidazole moiety in different fields of science highlights the necessity of designing and performing well-organized preparing procedures for the synthesis of corresponding highly substituted derivatives. In this regard, the MCRs of benzyl or benzoin with aldehydes, and primary amines or ammonium acetate is one of the most convenient protocols for synthesis of multi-substituted imidazole derivatives.\u003csup\u003e127\u0026ndash;130\u003c/sup\u003e Following this issue, numerous heterogenous or homogenous catalytic systems including ZSM-11 or HY zeolite, dimethylpyridinium trinitromethanide, 3-picolinic acid, silica sulfuric acid, ZrO\u003csub\u003e2\u003c/sub\u003e-Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, ZrO\u003csub\u003e2\u003c/sub\u003e-β-cyclodextrin, nano-Al-MCM-41, triethylammonium acetate as an ionic liquid, I\u003csub\u003e2\u003c/sub\u003e, Kegin-type hetero polyacids, chitosan-coated Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanoparticles, Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-PEG-Cu, Bohemite nanoparticles, silica choloride, 2,6-pyromellitic diamide\u0026ndash;diacid bridged mesoporous organosilica nanospheres, (N\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003eSiF\u003csub\u003e6\u003c/sub\u003e, magnetic polyborate nanoparticles\u003csup\u003e131\u003c/sup\u003e and Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e/SiO\u003csub\u003e2\u003c/sub\u003e decorated trimesic acid-melamine have been employed for the multi-component synthesis of desired imidazole derivatives \u003csup\u003e70,100,132\u0026ndash;136\u003c/sup\u003e. Although these mentioned methods have several advantages, they suffer from several disadvantages such as using hazardous or expensive reagents, pollution created during the catalyst preparation, low stability or recyclability of the catalysts and also low yields of the desired products, long reaction times and difficult work-up procedures. Therefore, designing and preparation of the productive, environmentally-benign and inexpensive methods for the synthesis of multi-substituted imidazoles would be very demanded\u003csup\u003e54\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eIn this research and in continuing our previous works\u003csup\u003e29,30,40\u003c/sup\u003e, we have reported a novel sustainable green nanomagnetic catalytic system (CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e catalyst, \u003cb\u003e1\u003c/b\u003e) based on modified naturally-occurring biopolymeric chitosan, by using methionine amino acid through grafting of EDTA dianhydride linker followed by Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e decoration. The catalyst (\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e) was examined in both 3- and 4-components reactions for successful synthesis of corresponding imidazole derivatives in high to excellent yields and short reaction time \u003cb\u003e(\u003c/b\u003eFig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e\u003cb\u003e)\u003c/b\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cp\u003e\u003cspan type=\"SmallCaps\" name=\"Emphasis\"\u003eThe prepared CS-EDTA-MET@\u003c/span\u003eFe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e \u003cspan type=\"SmallCaps\" name=\"Emphasis\"\u003eorganocatalyst\u003c/span\u003e (\u003cspan\u003e1\u003c/span\u003e) \u003cspan type=\"SmallCaps\" name=\"Emphasis\"\u003ewas characterized using various suitable techniques including FT-IR, FESEM, XRD, TGA and EDS.\u003c/span\u003e\u003c/p\u003e\n\u003cp\u003eFigure \u003cspan\u003e3\u003c/span\u003e shows the FT-IR spectra of chitosan (\u003cstrong\u003ea\u003c/strong\u003e) and CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (\u003cstrong\u003e1\u003c/strong\u003e, \u003cstrong\u003eb\u003c/strong\u003e). According to Fig. \u003cspan\u003e3\u003c/span\u003ea, the absorption bands at 3100\u0026ndash;3444 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are attributed to the stretching vibration of both O\u0026ndash;H and N\u0026ndash;H bonds of amine groups. Also, absorption band at 2923 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e belongs to the stretching vibration of C\u0026ndash;H aliphatic bonds. As shown in Fig. \u003cspan\u003e3\u003c/span\u003eb, the broad absorption bands at 2400\u0026ndash;3400 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are attributed to the stretching vibration of COOH functional groups. The absorption band at 588 is attributed to the Fe‒O bonds. Other functional groups including ester and amide are also observed in the FTIR spectrum but in lower intensities.\u003c/p\u003e\n\u003cp\u003eFigure \u003cspan\u003e4\u003c/span\u003e shows the EDS analysis related to the \u003cspan type=\"BoldSmallCaps\" name=\"Emphasis\"\u003eCS-EDTA-MET@\u003c/span\u003eFe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e organocatlyst (\u003cspan\u003e1\u003c/span\u003e), which confirms the presence of C, O, N, S and Fe elements in its structure. Also, the EDS mapping images shows the uniform particle distribution in the nanomaterial texture.\u003c/p\u003e\n\u003cp\u003eFESEM images of \u003cspan type=\"BoldSmallCaps\" name=\"Emphasis\"\u003eCS-EDTA-MET\u003c/span\u003e@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanomaterial (\u003cspan\u003e1\u003c/span\u003e) are shown in Fig. \u003cspan\u003e5\u003c/span\u003e. The FESEM images of the structure of \u003cspan type=\"BoldSmallCaps\" name=\"Emphasis\"\u003eCS-EDTA-MET\u003c/span\u003e@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e shows that the morphology of chitosan has changed from wide regular sheets to smaller irregular particles, which confirms the formation of the desired format. Also, these particles have a uniform dispersion and average particle size of 20\u0026ndash;55 nm.\u003c/p\u003e\n\u003cp\u003eUsing thermogravimetric analysis (TGA), the thermal stability of the prepared catalyst (\u003cspan\u003e1\u003c/span\u003e) was investigated in the temperature range of 50\u0026ndash;1000\u0026deg;C. As shown in Fig. \u003cspan\u003e6\u003c/span\u003e, two weight loss steps were observed between 250 and 400\u0026deg;C. Since the pristine chitosan is degraded at 200\u0026ndash;220\u0026deg;C\u003csup\u003e23\u003c/sup\u003e, This degradation at the temperature range of 250\u0026ndash;400\u0026deg;C indicates that DL-methionine is grafted properly to the chitosan backbone through EDTA linker, which affects the thermal stability of the chitosan and its degradation takes place at a higher temperature. Another weight loss can be seen from 400\u0026ndash;500\u0026deg;C, which is related to the total decomposition of the polymeric chain and carbon residue. The curve slope remains approximately constant from 500\u0026ndash;1000\u0026deg;C. This phenomenon shows the oxidation state of the inorganic magnetite.\u003c/p\u003e\n\u003cp\u003eFigure \u003cspan\u003e7\u003c/span\u003e shows the XRD pattern of \u003cspan type=\"BoldSmallCaps\" name=\"Emphasis\"\u003eCS-EDTA-MET\u003c/span\u003e@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (\u003cspan\u003e1\u003c/span\u003e). There are symmetrical reactions at 2\u0026theta; of 30.14\u0026deg;, 35.50\u0026deg;, 43.13\u0026deg;, 53.66\u0026deg;, 57.21\u0026deg;, and 62.71\u0026deg; which are characteristic of the \u003cspan type=\"BoldSmallCaps\" name=\"Emphasis\"\u003eCS-EDTA-MET\u003c/span\u003e@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (\u003cspan\u003e1\u003c/span\u003e) structure according to the standard XRD patterns of chitosan (JCPDS card no. 00-039-1894), DL-methionine (JCPDS card no. 00-005-0311) EDTA (JCPDS card no. 00-033-1672), and Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (JCPDS card no. 01-076-0956). As can be seen, the results obtained from the XRD pattern of \u003cspan type=\"BoldSmallCaps\" name=\"Emphasis\"\u003eCS-EDTA-MET\u003c/span\u003e@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (\u003cspan\u003e1\u003c/span\u003e). confirms the successful preparation of the desired nanomaterial.\u003c/p\u003e\n\u003cp\u003eThe VSM analysis has performed at room temperature by applying a magnetic field \u0026minus;\u0026thinsp;1000 to +\u0026thinsp;1000 oersted to measure the magnetic properties of the \u003cspan type=\"BoldSmallCaps\" name=\"Emphasis\"\u003eCS-EDTA-MET\u003c/span\u003e@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (\u003cspan\u003e1\u003c/span\u003e) nanocatalyst. As can be seen in Fig. \u003cspan\u003e8\u003c/span\u003e, the phenomenon of hysteresis was not observed, which shows no residual loop, and this feature demonstrates that no accumulation occurs in the presence of a magnetic field. Moreover, the (S) curve for \u003cspan type=\"BoldSmallCaps\" name=\"Emphasis\"\u003eCS-EDTA-MET\u003c/span\u003e@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (\u003cspan\u003e1\u003c/span\u003e) nanocatalyst confirms excellent paramagnetic behaviour without any hindrance or reluctance. In fact, the maximum magnetic saturation (Ms) is 18.57 emu/g. and this magnetic property of the \u003cspan type=\"BoldSmallCaps\" name=\"Emphasis\"\u003eCS-EDTA-MET\u003c/span\u003e@-Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (\u003cspan\u003e1\u003c/span\u003e) nanocatalyst is enough to be easily separated from the reaction mixture by an external magnet.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eOptimization of conditions for the synthesis of imidazole derivatives in the presence of CS-EDTA-MET@Fe\u003c/strong\u003e \u003csub\u003e\u0026nbsp;\u003cstrong\u003e3\u003c/strong\u003e\u0026nbsp;\u003c/sub\u003e \u003cstrong\u003eO\u003c/strong\u003e \u003csub\u003e\u0026nbsp;\u003cstrong\u003e4\u003c/strong\u003e\u0026nbsp;\u003c/sub\u003e \u003cstrong\u003eorganocatalyst\u003c/strong\u003e (\u003cspan\u003e1\u003c/span\u003e).\u003c/p\u003e\n\u003cp\u003eIn this section, the efficacy of CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanomaterial (\u003cspan\u003e1\u003c/span\u003e) in the model reaction for the synthesis of 2,4,5-trisubstituted imidazole derivatives were explored. Therefore, different parameters including solvent, catalyst loading, temperature, and reaction time were investigated to determine the optimal reaction conditions (Table \u003cspan\u003e1\u003c/span\u003e). The model reaction was examined by using benzoin (\u003cstrong\u003e2\u003c/strong\u003e, 1.0 mmol),4-chlorobenzaldehyde (\u003cstrong\u003e3a\u003c/strong\u003e, 1.0 mmol), and ammonium acetate (\u003cstrong\u003e4\u003c/strong\u003e, 3.0 mmol) in the presence of CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanomaterial (\u003cspan\u003e1\u003c/span\u003e) for the synthesis of imidazole derivatives in various conditions. The results are summarized in Table \u003cspan\u003e1\u003c/span\u003e. The amount of the catalyst \u003cstrong\u003e1\u003c/strong\u003e plays an essential role in the model reaction. Indeed, the reaction in the absence of the CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e affords a poor yield of the desired 2-(4-chlorophenyl)-4,5-diphenyl-1\u003cem\u003eH\u003c/em\u003e-imidazole (\u003cstrong\u003e5a\u003c/strong\u003e) after 360 min under reflux conditions (\u003cstrong\u003eentry 1\u003c/strong\u003e, Table \u003cspan\u003e1\u003c/span\u003e). Moreover, the effect of other solvents including solvent-free conditions, H\u003csub\u003e2\u003c/sub\u003eO, MeOH, MeCN and EtOAc were also studied on the progress of the model reaction under same catalyst loading (entries 2\u0026ndash;9). The highest yield of the desired product \u003cstrong\u003e5a\u003c/strong\u003e was obtained by using 10 mg of catalyst loading \u003cstrong\u003e1\u003c/strong\u003e in EtOH at 60 \u003csup\u003eo\u003c/sup\u003eC (\u003cstrong\u003eentry 12\u003c/strong\u003e, Table \u003cspan\u003e1\u003c/span\u003e). Consequently, among all the screened solvents EtOH was selected as the optimal solvent in the next experiments. The effect of lower catalyst loadings than 10 mg in different conditions were further studied (\u003cstrong\u003eentries 2\u0026ndash;12\u003c/strong\u003e). Moderate yields of the desired product \u003cstrong\u003e5a\u003c/strong\u003e were obtained in all studied cases. The progress of the model reaction to afford the desired product \u003cstrong\u003e5a\u003c/strong\u003e in EtOH were investigated in the presence of catalyst precursors as well to show their synergistic effects on the catalytic activity (Table \u003cspan\u003e1\u003c/span\u003e, \u003cstrong\u003eentries 14\u0026ndash;18\u003c/strong\u003e). Based on the obtained results, the best conditions for this transformation is mentioned in \u003cstrong\u003eentry 13\u003c/strong\u003e.\u003c/p\u003e\n\u003cp\u003eThe optimized reaction conditions (10 mg of CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e catalyst loading \u003cstrong\u003e1\u003c/strong\u003e, EtOH at 60 \u003csup\u003eo\u003c/sup\u003eC) were developed to other aromatic carbocyclic aldehydes \u003cstrong\u003e3b-k\u003c/strong\u003e. The results are summarized in Table \u003cspan\u003e2\u003c/span\u003e. The studied aldehydes well survived under the optimized conditions to afford their corresponding 2,4,5-trisubstituted imidazole derivatives \u003cstrong\u003e3b-k\u003c/strong\u003e in high to excellent yields. By adjusting the same reaction conditions for the four-component synthesis of imidazole derivatives, the fascinating results for 1,2,4,5-trisubstituted imidazole derivatives \u003cstrong\u003e7a-u\u003c/strong\u003e were obtained which are mentioned in Table \u003cspan\u003e3\u003c/span\u003e. In this section of our study, a wide range of 1,2,4,5-trisubstituted imidazole derivatives were prepared by altering both aromatic carbocyclic aldehydes \u003cstrong\u003e3\u003c/strong\u003e as well as primary amine source as one of the reaction component.\u003c/p\u003e\n\u003cp\u003eIn general, aromatic aldehydes bearing electron withdrawing groups such as Cl, Br and NO\u003csub\u003e2\u003c/sub\u003e afford their corresponding imidazole derivatives \u003cstrong\u003e5\u003c/strong\u003e or \u003cstrong\u003e7\u003c/strong\u003e at higher yields compared to those containing electron releasing substituents such as Me, OH, OMe and NMe\u003csub\u003e2\u003c/sub\u003e substituents.\u003c/p\u003e\n\u003cp\u003eThe most plausible mechanisms for the synthesis of tri- and tetra-substituted imidazoles \u003cstrong\u003e5\u003c/strong\u003e or \u003cstrong\u003e7\u003c/strong\u003e catalyzed by the CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanomaterial (\u003cspan\u003e1\u003c/span\u003e) have been illustrated in (Fig. \u003cspan\u003e9\u003c/span\u003e\u003cstrong\u003e)\u003c/strong\u003e. Indeed, the carbonyl groups of aldehydes \u003cstrong\u003e3\u003c/strong\u003e is activated by interaction with the Lewis acidic centers including Fe ions as well as hydrogen donors of catalyst (\u003cspan\u003e1\u003c/span\u003e). Then, nucleophiles including ammonia (\u003cspan\u003e4\u003c/span\u003e) and amines \u003cstrong\u003e6\u003c/strong\u003e can be added to the activated carbonyl group of aldehydes \u003cstrong\u003e3\u003c/strong\u003e to create the corresponding imine \u003cstrong\u003eI\u003c/strong\u003e and aminal \u003cstrong\u003eII\u003c/strong\u003e intermediates, respectively. After that, the aminal intermediate \u003cstrong\u003eII\u003c/strong\u003e reacts with the activated carbonyl group of benzoin (\u003cspan\u003e2\u003c/span\u003e) to afford cyclic intermediate \u003cstrong\u003eIII\u003c/strong\u003e. This intermediate is formed by losing one molecules of water through simple imine condensation and subsequent air oxidation. Desired imidazole derivatives \u003cstrong\u003e5\u003c/strong\u003e or \u003cstrong\u003e7\u003c/strong\u003e are finally produced after a [1,5-H] shift in the structure of intermediate \u003cstrong\u003eIV\u003c/strong\u003e and liberates the catalyst (\u003cspan\u003e1\u003c/span\u003e) to start a new cycle of its catalytic activity.\u003csup\u003e100,136,148\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eOne of the merits of heterogeneous nanomagnetic catalytic systems is their easy separation from the reaction mixture by means of an external magnet bar and subsequent reusing in the next designated catalytic-promoted transformations, which make them appropriate candidates for further applications in the relevant industrial process. In this part of our study, the reusability of CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanocatalyst (\u003cspan\u003e1\u003c/span\u003e) was investigated in the model reaction for further five runs. After completion of the reaction in each run, the nanocatalyst \u003cstrong\u003e1\u003c/strong\u003e was separated from the reaction mixture by using an external magnet and washed with EtOH. Then, it was dried in an oven at 70\u0026deg;C for 1 h. The recycled catalyst \u003cstrong\u003e1\u003c/strong\u003e was utilized for more five consecutive runs in the model reaction. The results are summarized in Fig. \u003cspan\u003e10\u003c/span\u003e. To our delight, the catalytic activity of the novel heterogeneous catalyst did not change significantly after six consecutive runs and only a little loss in the final yields was observed.\u003c/p\u003e\n\u003cp\u003eTable \u003cspan\u003e4\u003c/span\u003e compares the efficiency of CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e organocatalyst (\u003cspan\u003e1\u003c/span\u003e) with other catalysts for the synthesis of imidazole derivatives \u003cstrong\u003e5a\u003c/strong\u003e. For this comparison, several parameters, e.g., the reaction time, temperature, and the reaction yield, were taken into account. It can be implied that CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e heterogeneous catalyst (\u003cspan\u003e1\u003c/span\u003e) showed better performance than previously reported catalytic systems for the synthesis of imidazole derivatives.\u003c/p\u003e\n\u003cdiv\u003e\n \u003ctable id=\"Tab4\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv\u003eTable 4\u003c/div\u003e\n \u003cdiv\u003e\n \u003cp\u003eComparative results of the activity of different catalysts for the synthesis of \u003cstrong\u003e5a\u003c/strong\u003e\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eEntry\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eCatalyst\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eCatalyst loading\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eReaction conditions\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eTime (min)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3-Picolinic acid\u003csup\u003e70\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e12 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEtOH/80\u0026deg;C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e120\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003ePANI-FeCl\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e149\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e200 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCH\u003csub\u003e3\u003c/sub\u003eCN/ Reflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1440\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003ePMAMOSa\u003csup\u003e100\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEtOH/\u003c/p\u003e\n \u003cp\u003eReflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e45\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eNano- TiCl\u003csub\u003e4\u003c/sub\u003e.SiO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e150\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e100 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eSolvent-free/\u003c/p\u003e\n \u003cp\u003e130\u0026deg;C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e30\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eK\u003csub\u003e5\u003c/sub\u003eCoW\u003csub\u003e12\u003c/sub\u003eO\u003csub\u003e40\u003c/sub\u003e\u0026middot;3H\u003csub\u003e2\u003c/sub\u003eO\u003csup\u003e151\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e32\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eSolvent-free/140\u0026deg;C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e180\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eSulfonic acid functionalized silica\u003csup\u003e152\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e20 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eSolvent-free/140\u0026deg;C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e100\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eCS-EDTA-MET@Fe\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e10 mg\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eEtOH/ 60\u0026deg;C\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e45\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e"},{"header":"Conclusions","content":"\u003cp\u003eIn summary, we have developed an effective and practical procedure for the synthesis of both tri- and tetra-substituted imidazole derivatives in the presence of DL-methionine grafted to chitosan by EDTA linker (CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e) nanomaterial, as a heterogeneous magnetic organocatalyst, via the one-pot three and/or four-component condensation of benzoin, aromatic aldehydes, and amine sources. A wide range of desired products were smoothly prepared in high to excellent yields under low catalyst loading of CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanocatalyst and green conditions. The advantages of this method include appropriate catalytic activity, easy separation and reusability of the catalyst, high to excellent yield of products, use of green solvent, and mild reaction conditions. Moreover, this magnetic organocatalyst was recovered and reused at least five times without significant decrease in its activity. Additionally, the use of chitosan biopolymer in a modified form provides advantages in terms of the use of renewable feedstock as well as low toxic and biodegradable material in design and application of nano-ordered heterogeneous organocatalytic systems.\u003c/p\u003e"},{"header":"Experimental section","content":"\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003eReagents and Instruments\u003c/h2\u003e \u003cp\u003eAll the materials of this research as well as the reagents were purchased from Merck and Aldrich and were used in the processes without further purification, except for benzaldehyde, which was used as a freshly distilled sample. DL-methionine (MW\u0026thinsp;=\u0026thinsp;149.21 g.mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) was purchased from an approved local supplier. Chitosan (CS, degree of deacetylation\u0026thinsp;=\u0026thinsp;82\u0026thinsp;\u0026plusmn;\u0026thinsp;2%, MW\u0026thinsp;=\u0026thinsp;100\u0026ndash;300 kDa) was Purchased from Acros Organics. Characterization of the CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e) was carried out using FESEM TESCAN-MIRA3, EDX Numerix DXP-X10P and TGA Bahr Company STA 504. FT-IR spectra were recorded as KBr pellets on a Perkin Elmer, 1720-X model (USA) spectrometer. \u003csup\u003e1\u003c/sup\u003eH NMR spectra (500 MHz) were obtained using Bruker DRX-500 Avance spectrometer in CDCl3 or DMSO‑d6, as solvent, at ambient temperature. To monitor the reactions progress, analytical thin layer chromatography (TLC) was performed using Merck 60 F-254 Al 0.2 mm silica gel plates. All yields refer to the isolated products. All the products are known compounds and were identified by comparison of their physical, spectroscopic and analytical data with the authentic samples. All products were characterized by spectroscopic methods (FTIR and \u003csup\u003e1\u003c/sup\u003eHNMR spectra) as well as measurement of melting points.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003ePreparation of the catalyst CS-EDTA-MET@FeO nanomaterial (1)\u003c/h3\u003e\n\u003cp\u003eThe procedure for preparation of the catalytic system is illustrated in \u003cb\u003eFig\u003c/b\u003e. \u003cb\u003eS1\u003c/b\u003e.\u003c/p\u003e\n\u003ch3\u003eGeneral procedure for preparation of EDTA dianhydride (EDTADA)\u003c/h3\u003e\n\u003cp\u003e \u003cdiv class=\"BlockQuote\"\u003e \u003cp\u003eEDTA (10.0 g, 34 mmol), pyridine (16 mL), and acetic anhydride (14 mL) were charged into a 100 mL round bottom flask equipped with a condenser and a magnetic stirrer. The reaction was mixed and stirred at 65\u0026ndash;70\u0026deg;C for 24 h under an Ar atmosphere. After completion of the reaction, the suspension was filtered and the crude product was washed carefully with acetic anhydride and dry diethyl ether under a stream of Ar to afford a white powder. The final product was dried by a rotary evaporator under vacuum at 40\u0026ndash;50\u0026deg;C until getting fine and dry white powder (yield 90\u0026ndash;92%, mp: 189\u0026ndash;191 \u003csup\u003eo\u003c/sup\u003eC (\u003cb\u003eScheme 3\u003c/b\u003e).\u003csup\u003e153\u003c/sup\u003e\u003c/p\u003e \u003c/div\u003e \u003c/p\u003e\n\u003ch3\u003ePreparation of the DL-methionine-EDTA monoanhydride (MET-MAEDTA)\u003c/h3\u003e\n\u003cp\u003eEDTADA (0.256 g, 1.0 mmol) was charged into a 25 mL two-neck round-bottom flask equipped with a reflux condenser and a magnet bar. Then, 3 ml of dry toluene was added under an Ar atmosphere. In addition, exactly one equivalent of DL-methionine (0.149 g, 1.0 mmol in 6.0 mL of toluene) was gradually added over 60 min. to control the selective reaction with one side of EDTADA. After that, the mixture was refluxed under constant stirring and Ar atmosphere for 18 h. Finally, the desired intermediate (\u003cb\u003eI\u003c/b\u003e) was filtered and dried under vacuum at 60\u0026deg;C by using a rotary evaporator to afford a creamy white powder (0.394 g, Yield\u0026thinsp;=\u0026thinsp;92.6%).\u003csup\u003e21,30\u003c/sup\u003e\u003c/p\u003e\n\u003ch3\u003ePreparation of DL-methionine-ETDA grafted on chitosan (CS-EDTA-MET)\u003c/h3\u003e\n\u003cp\u003e \u003cdiv class=\"BlockQuote\"\u003e \u003cp\u003eIntermediate \u003cb\u003eI\u003c/b\u003e (0.16 g) and (chitosan, 0.32g) were charged into a 25 mL double-neck round-bottom flask containing dry toluene (10 mL). Then, the obtained mixture was stirred and heated at 60\u0026ndash;70\u0026deg;C under an Ar atmosphere for 18 h. After completion of the reaction, the temperature cooled down to r.t. and the suspension was filtered and dried in a vacuum oven to afford (0.45 g, 93.75%) of the desired intermediate (\u003cb\u003eII\u003c/b\u003e).\u003c/p\u003e \u003c/div\u003e \u003c/p\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003ePreparation of the CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e catalyst (\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e)\u003c/h2\u003e \u003cp\u003e \u003cdiv class=\"BlockQuote\"\u003e \u003cp\u003e0.127 g of obtained CS-EDTA-MET was charged into a 250 mL two-neck round-bottom flask containing 10 mL water and heat to 70\u0026deg;C, then a mixture of (FeCl\u003csub\u003e2\u003c/sub\u003e:4H\u003csub\u003e2\u003c/sub\u003eO, 0.11 g and FeCl\u003csub\u003e3\u003c/sub\u003e:6H\u003csub\u003e2\u003c/sub\u003eO, 0.22 g) was added to the flask under inert Ar atmosphere followed by heating at 75\u0026deg;C for 10 min. After that, (NH\u003csub\u003e3\u003c/sub\u003e 25%, 5 mL) was added dropwise under vigorous mixing and Ar atmosphere. The mixture colour turns black immediately. The suspension was mixed for more 2 h under mentioned conditions. The product was washed several times with 25 mL of deionized water to reach the pH range of 5\u0026ndash;6. Finally the product was washed with EtOH and dried at 70\u0026deg;C to get 0.20 g of the magnetic catalyst (\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e) (\u003cb\u003eFig\u003c/b\u003e. \u003cb\u003eS1)\u003c/b\u003e.\u003c/p\u003e \u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eGeneral Procedure for the Synthesis of tri- and tetra-substituted imidazole derivatives 5 or 7 in the presence of CS-EDTA-MET@Fe\u003c/b\u003e \u003csub\u003e \u003cb\u003e3\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO\u003c/b\u003e \u003csub\u003e \u003cb\u003e4\u003c/b\u003e \u003c/sub\u003e (\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e)\u003c/p\u003e \u003cp\u003eIn a 10 mL flask, benzoin (\u003cb\u003e2\u003c/b\u003e, 1.0 mmol, 0.21 g), aldehyde (\u003cb\u003e3\u003c/b\u003e, 1.0 mmol, 0.14 g), and ammonium acetate (\u003cb\u003e4\u003c/b\u003e, 3.0 mmol, 0.23g) or/and amine (6, 1.0 mmol, 0.93 g) along with 0.01 g of CS-EDTA-MET@Fe3O4 (\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e) were added to EtOH 96% (5 mL). The obtained mixture was heated at 60\u0026deg;C for appropriate time mentioned in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. The progress of the reaction was monitored by thin layer chromatography (TLC) with EtOAc and n-hexane (3:1 V/V). After the completion of reaction, 5.0 mL of EtOH was added to the reaction mixture and heated to make a clear solution. After that, it was filtered off to separate the CS-EDTA-MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e) by using an external magnet. The filtrate was cooled and allowed to give pure product \u003cb\u003e5\u003c/b\u003e or \u003cb\u003e7\u003c/b\u003e by the crystallization method in the refrigerator. The crystals were collected by vacuum filtration, washed with EtOH and dried at 70\u0026deg;C for 1 h.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003eSelected spectral data\u003c/h2\u003e \u003cp\u003e \u003cb\u003e4,5Diphenyl-2(\u003c/b\u003e \u003cb\u003ep\u003c/b\u003e \u003cb\u003etolyl)-1\u003c/b\u003e \u003cb\u003eH\u003c/b\u003e \u003cb\u003eimidazole\u003c/b\u003e (\u003cb\u003e5e\u003c/b\u003e)\u003c/p\u003e \u003cp\u003eWhite solid; Yield 92%, mp 230\u0026ndash;232\u0026deg;C (Lit. mp 232\u0026ndash;234\u0026deg;C); \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e ): δ 2.42 (s, 3H, Me), 7.28\u0026ndash;7.37 (m, 8H, Ar), 7.56 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;7.2 Hz, 4H, Ar), 7.82 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.4 Hz, 2H, Ar).\u003c/p\u003e \u003cp\u003e \u003cb\u003e2(4Methoxyphenyl)-4,5diphenyl-1\u003c/b\u003e \u003cb\u003eH\u003c/b\u003e \u003cb\u003eimidazole\u003c/b\u003e(\u003cb\u003e5f\u003c/b\u003e)\u003c/p\u003e \u003cp\u003eWhite solid; Yield 93%, mp 226\u0026ndash;229\u0026deg;C (Lit. mp 228\u0026ndash;230\u0026deg;C); \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e ): δ 3.88 (s, 3H,OMe), 6.99 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.4 Hz, 2H, Ar), 7.30\u0026ndash;7.77 (m, 10H, Ar), 7.86 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.8 Hz, 2H, Ar), 9.47 (brs, 1H, NH).\u003c/p\u003e \u003cp\u003e \u003cb\u003e2-(3-Nitrophenyl)-1,4,5-triphenyl-1\u003c/b\u003e \u003cb\u003eH\u003c/b\u003e \u003cb\u003e-imidazole\u003c/b\u003e (\u003cb\u003e7b\u003c/b\u003e)\u003c/p\u003e \u003cp\u003eMp: 249\u0026ndash;251\u0026deg;C; Yellow solid; FTIR (KBr; cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e): 3427, 1525, 1344, 766, 697; \u003csup\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sup\u003eH NMR (500 MHz, DMSO-\u003cem\u003ed\u003c/em\u003e\u003csub\u003e6\u003c/sub\u003e, ppm): δ 8.97 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;2.3 Hz, 1H), 8.53 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;7.9 Hz, 1H), 8.23 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.3 Hz, 1H), 8.18\u0026ndash;8.13 (m, 1H), 7.80 (td, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.2, 1.7 Hz, 1H), 7.61\u0026ndash;7.26 (m, 14H).\u003c/p\u003e \u003cp\u003e \u003cb\u003eN\u003c/b\u003e,\u003cb\u003eN\u003c/b\u003e\u003cb\u003e-Dimethyl-4-(1,4,5-triphenyl-1\u003c/b\u003e\u003cb\u003eH\u003c/b\u003e\u003cb\u003e-imidazol-2-yl)aniline\u003c/b\u003e (\u003cb\u003e7g\u003c/b\u003e)\u003c/p\u003e \u003cp\u003eMp: 205\u0026ndash;207\u0026deg;C; Brown solid; FTIR (KBr; cm-1): 3422, 2926, 2364, 1722, 1612, 1488, 1442, 1370, 816, 694; \u003csup\u003e1\u003c/sup\u003eH NMR (500 MHz, DMSO-\u003cem\u003ed\u003c/em\u003e\u003csub\u003e6\u003c/sub\u003e, ppm): δ 7.60\u0026ndash;7.50 (m, 1H), 7.46 (d, J\u0026thinsp;=\u0026thinsp;8.0 Hz, 2H), 7.37\u0026ndash;7.31 (m, 4H), 7.21 (m, 10H), 6.56 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.0 Hz, 2H), 2.86 (s, 6H).\u003c/p\u003e \u003cp\u003e \u003cb\u003e2-(4-Methoxyphenyl)-4,5-diphenyl-1-(\u003c/b\u003e \u003cb\u003ep\u003c/b\u003e \u003cb\u003e-tolyl)-1\u003c/b\u003e \u003cb\u003eH\u003c/b\u003e \u003cb\u003e-imidazole\u003c/b\u003e (\u003cb\u003e7m\u003c/b\u003e).\u003c/p\u003e \u003cp\u003eMp: 178\u0026ndash;181\u0026deg;C; White solid; FTIR (KBr; cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e): 2922, 2376, 1606, 1514, 1438, 1368, 1022, 824, 776, 698, 526; \u003csup\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sup\u003eH NMR (500 MHz, DMSO-\u003cem\u003ed\u003c/em\u003e\u003csub\u003e6\u003c/sub\u003e, ppm): δ 7.50\u0026ndash;7.47 (m, 2H), 7.35\u0026ndash;7.30 (m, 5H), 7.25\u0026ndash;7.22 (m, 4H), 7.18\u0026ndash;7.11 (m, 5H), 6.89\u0026ndash;6.85 (m, 2H), 3.74 (s, 3H), 2.27 (s, 3H).\u003c/p\u003e \u003cp\u003e \u003cb\u003e1-Benzyl-2-(4-methoxyphenyl)-4,5-diphenyl-1\u003c/b\u003e \u003cb\u003eH\u003c/b\u003e \u003cb\u003e-imidazole\u003c/b\u003e (\u003cb\u003e7t\u003c/b\u003e)\u003c/p\u003e \u003cp\u003eMp: 156\u0026ndash;159\u0026deg;C; White solid; FTIR (KBr; cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e): 3026, 2929, 2361, 1605, 1530, 1482, 1449; \u003csup\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sup\u003eH NMR (500 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e, ppm): δ 7.60\u0026ndash;7.57 (m, 3H), 7.35\u0026ndash;7.14 (m, 12H), 6.92 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.8 Hz, 2H), 6.82 (dd, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;7.7, 1.7 Hz, 2H), 5.09 (s, 2H), 3.86\u0026ndash;3.78 (m, 3H).\u003c/p\u003e \u003c/div\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll data generated or analyzed during this study are included in this published article [and its supplementary information files].\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eContributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMohammad Dohendou\u003c/strong\u003e: Methodology,\u0026nbsp;Investigation, Formal analysis, Writing-original draft;\u0026nbsp;\u003cstrong\u003eMohammad G. Dekamin\u003c/strong\u003e:\u0026nbsp;Conceptualization, Resources,\u0026nbsp;Project planning, Supervision, Financial, Editing-Final draft; \u003cstrong\u003eZahra Dehnamaki\u003c/strong\u003e:\u0026nbsp;Investigation, Formal analysis, Writing-original draft;\u0026nbsp;\u003cstrong\u003eDanial Namaki\u003c/strong\u003e:\u0026nbsp;Investigation, Formal analysis, Writing-original draft;\u0026nbsp;\u003cstrong\u003eSuranjana V. Mayani\u003c/strong\u003e:\u0026nbsp;Editing-Final draft,\u0026nbsp;Methodology,\u0026nbsp;Formal analysis.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflict of interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that there are no conflicts of interest regarding the publication of this manuscript.\u003c/p\u003e\n\u003cp\u003eAcknowledgments\u003c/p\u003e\n\u003cp\u003eWe are grateful for the financial support from The Research Council of Iran University of Science and Technology (IUST), Tehran, Iran (Grant No. 160/23372). We would also like to acknowledge the support of The Iran Nanotechnology Initiative Council (INIC), Iran. Suranjana V. Mayani would also like to acknowledge Marwadi University, Rajkot, Gujarat, India.\u0026nbsp;\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eRai, P. K.\u003cem\u003e et al.\u003c/em\u003e Nanoparticle-plant interaction: Implications in energy, environment, and agriculture. \u003cem\u003eEnvironment international\u003c/em\u003e \u003cstrong\u003e119\u003c/strong\u003e, 1-19 (2018).\u003c/li\u003e\n\u003cli\u003eVillalba-Rodr\u0026iacute;guez, A. M.\u003cem\u003e et al.\u003c/em\u003e Nanomaterial Constructs for Catalytic Applications in Biomedicine: Nanobiocatalysts and Nanozymes. \u003cem\u003eTopics in Catalysis\u003c/em\u003e \u003cstrong\u003e66\u003c/strong\u003e, 707-722, doi:10.1007/s11244-022-01766-4 (2023).\u003c/li\u003e\n\u003cli\u003eZhu, L.\u003cem\u003e et al.\u003c/em\u003e Tannic acid modified keratin/sodium alginate/carboxymethyl chitosan biocomposite hydrogels with good mechanical properties and swelling behavior. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e14\u003c/strong\u003e, 12864, doi:10.1038/s41598-024-63186-6 (2024).\u003c/li\u003e\n\u003cli\u003eAl-Azmi, A. \u0026amp; Keshipour, S. Cross-linked chitosan aerogel modified with Pd(II)/phthalocyanine: Synthesis, characterization, and catalytic application. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e9\u003c/strong\u003e, 13849, doi:10.1038/s41598-019-50021-6 (2019).\u003c/li\u003e\n\u003cli\u003eAhmed, M. E., Mohamed, M. I., Ahmed, H. Y., Elaasser, M. M. \u0026amp; Kandile, N. G. Fabrication and characterization of unique sustain modified chitosan nanoparticles for biomedical applications. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e14\u003c/strong\u003e, 13869, doi:10.1038/s41598-024-64017-4 (2024).\u003c/li\u003e\n\u003cli\u003eFranco, F., Rettenmaier, C., Jeon, H. S. \u0026amp; Roldan Cuenya, B. Transition metal-based catalysts for the electrochemical CO2 reduction: from atoms and molecules to nanostructured materials. \u003cem\u003eChemical Society Reviews\u003c/em\u003e \u003cstrong\u003e49\u003c/strong\u003e, 6884-6946, doi:10.1039/D0CS00835D (2020).\u003c/li\u003e\n\u003cli\u003eZheng, B.\u003cem\u003e et al.\u003c/em\u003e Rare-Earth Doping in Nanostructured Inorganic Materials. \u003cem\u003eChemical Reviews\u003c/em\u003e \u003cstrong\u003e122\u003c/strong\u003e, 5519-5603, doi:10.1021/acs.chemrev.1c00644 (2022).\u003c/li\u003e\n\u003cli\u003eShang, X., Yang, X., Liu, G., Zhang, T. \u0026amp; Su, X. A molecular view of single-atom catalysis toward carbon dioxide conversion. \u003cem\u003eChemical Science\u003c/em\u003e \u003cstrong\u003e15\u003c/strong\u003e, 4631-4708, doi:10.1039/D3SC06863C (2024).\u003c/li\u003e\n\u003cli\u003eMohan, A., Jaison, A. \u0026amp; Lee, Y.-C. Emerging trends in mesoporous silica nanoparticle-based catalysts for CO2 utilization reactions. \u003cem\u003eInorganic Chemistry Frontiers\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 3171-3194, doi:10.1039/D3QI00378G (2023).\u003c/li\u003e\n\u003cli\u003eJagadeesan, D. Multifunctional nanocatalysts for tandem reactions: A leap toward sustainability. \u003cem\u003eApplied Catalysis A: General\u003c/em\u003e \u003cstrong\u003e511\u003c/strong\u003e, 59-77, doi:https://doi.org/10.1016/j.apcata.2015.11.033 (2016).\u003c/li\u003e\n\u003cli\u003eQin, Z. Nanostructure Design of Catalysts: Latest Advances and Prospects. \u003cem\u003eNanomaterials (Basel)\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, doi:10.3390/nano13131980 (2023).\u003c/li\u003e\n\u003cli\u003eDohendou, M., Pakzad, K., Nezafat, Z., Nasrollahzadeh, M. \u0026amp; Dekamin, M. G. Progresses in chitin, chitosan, starch, cellulose, pectin, alginate, gelatin and gum based (nano)catalysts for the Heck coupling reactions: A review. \u003cem\u003eInternational Journal of Biological Macromolecules\u003c/em\u003e \u003cstrong\u003e192\u003c/strong\u003e, 771-819, doi:https://doi.org/10.1016/j.ijbiomac.2021.09.162 (2021).\u003c/li\u003e\n\u003cli\u003eMahadevan, R., Palanisamy, S. \u0026amp; Sakthivel, P. Role of nanoparticles as oxidation catalyst in the treatment of textile wastewater: Fundamentals and recent advances. \u003cem\u003eSustainable Chemistry for the Environment\u003c/em\u003e \u003cstrong\u003e4\u003c/strong\u003e, 100044, doi:https://doi.org/10.1016/j.scenv.2023.100044 (2023).\u003c/li\u003e\n\u003cli\u003eBaig, N., Kammakakam, I. \u0026amp; Falath, W. Nanomaterials: a review of synthesis methods, properties, recent progress, and challenges. \u003cem\u003eMaterials Advances\u003c/em\u003e \u003cstrong\u003e2\u003c/strong\u003e, 1821-1871, doi:10.1039/D0MA00807A (2021).\u003c/li\u003e\n\u003cli\u003eShetty, A., Molahalli, V., Sharma, A. \u0026amp; Hegde, G. Biomass-Derived Carbon Materials in Heterogeneous Catalysis: A Step towards Sustainable Future. \u003cem\u003eCatalysts\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e (2023).\u003c/li\u003e\n\u003cli\u003eQiu, M., Zhan, S., Yu, H., Zhu, D. \u0026amp; Wang, S. Facile preparation of ordered mesoporous MnCo2O4 for low-temperature selective catalytic reduction of NO with NH3. \u003cem\u003eNanoscale\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 2568-2577, doi:10.1039/C4NR06451H (2015).\u003c/li\u003e\n\u003cli\u003eSharma, N., Ojha, H., Bharadwaj, A., Pathak, D. P. \u0026amp; Sharma, R. K. Preparation and catalytic applications of nanomaterials: a review. \u003cem\u003eRSC Advances\u003c/em\u003e \u003cstrong\u003e5\u003c/strong\u003e, 53381-53403, doi:10.1039/C5RA06778B (2015).\u003c/li\u003e\n\u003cli\u003eChng, L. L., Erathodiyil, N. \u0026amp; Ying, J. Y. Nanostructured Catalysts for Organic Transformations. \u003cem\u003eAccounts of Chemical Research\u003c/em\u003e \u003cstrong\u003e46\u003c/strong\u003e, 1825-1837, doi:10.1021/ar300197s (2013).\u003c/li\u003e\n\u003cli\u003eZhang, Y.\u003cem\u003e et al.\u003c/em\u003e Nanostructured single-atom catalysts derived from natural building blocks. \u003cem\u003eEES Catalysis\u003c/em\u003e \u003cstrong\u003e2\u003c/strong\u003e, 475-506, doi:10.1039/D3EY00265A (2024).\u003c/li\u003e\n\u003cli\u003eKarami, S., Dekamin, M. G., Valiey, E. \u0026amp; Shakib, P. DABA MNPs: A new and efficient magnetic bifunctional nanocatalyst for the green synthesis of biologically active pyrano [2, 3-c] pyrazole and benzylpyrazolyl coumarin derivatives. \u003cem\u003eNew Journal of Chemistry\u003c/em\u003e \u003cstrong\u003e44\u003c/strong\u003e, 13952-13961 (2020).\u003c/li\u003e\n\u003cli\u003eRostami, N., Dekamin, M. G. \u0026amp; Valiey, E. Chitosan-EDTA-Cellulose bio-based network: A recyclable multifunctional organocatalyst for green and expeditious synthesis of Hantzsch esters. \u003cem\u003eCarbohydrate Polymer Technologies and Applications\u003c/em\u003e \u003cstrong\u003e5\u003c/strong\u003e, 100279, doi:https://doi.org/10.1016/j.carpta.2022.100279 (2023).\u003c/li\u003e\n\u003cli\u003eValiey, E., Dekamin, M. G. \u0026amp; Alirezvani, Z. Melamine-modified chitosan materials: An efficient and recyclable bifunctional organocatalyst for green synthesis of densely functionalized bioactive dihydropyrano[2,3-c]pyrazole and benzylpyrazolyl coumarin derivatives. \u003cem\u003eInternational Journal of Biological Macromolecules\u003c/em\u003e \u003cstrong\u003e129\u003c/strong\u003e, 407-421, doi:https://doi.org/10.1016/j.ijbiomac.2019.01.027 (2019).\u003c/li\u003e\n\u003cli\u003eSourkouhi, R. P., Dekamin, M. G., Valiey, E. \u0026amp; Dohendou, M. Magnetic decorated 5-sulfosalicylic acid grafted to chitosan: A solid acid organocatalyst for green synthesis of quinazoline derivatives. \u003cem\u003eCarbohydrate Polymer Technologies and Applications\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 100420, doi:https://doi.org/10.1016/j.carpta.2023.100420 (2024).\u003c/li\u003e\n\u003cli\u003eIlkhanizadeh, S., Khalafy, J. \u0026amp; Dekamin, M. G. Sodium alginate: A biopolymeric catalyst for the synthesis of novel and known polysubstituted pyrano[3,2-c]chromenes. \u003cem\u003eInternational Journal of Biological Macromolecules\u003c/em\u003e \u003cstrong\u003e140\u003c/strong\u003e, 605-613, doi:https://doi.org/10.1016/j.ijbiomac.2019.08.154 (2019).\u003c/li\u003e\n\u003cli\u003eDekamin, M. G.\u003cem\u003e et al.\u003c/em\u003e Sodium alginate: An efficient biopolymeric catalyst for green synthesis of 2-amino-4H-pyran derivatives. \u003cem\u003eInternational Journal of Biological Macromolecules\u003c/em\u003e \u003cstrong\u003e87\u003c/strong\u003e, 172-179, doi:https://doi.org/10.1016/j.ijbiomac.2016.01.080 (2016).\u003c/li\u003e\n\u003cli\u003eHong, M.\u003cem\u003e et al.\u003c/em\u003e One-pot cascade production of 2,5-diformylfuran from glucose over catalysts from renewable resources. \u003cem\u003eCatalysis Science \u0026amp; Technology\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 1335-1344, doi:10.1039/D2CY02017C (2023).\u003c/li\u003e\n\u003cli\u003eRostami, N., Dekamin, M. G., Valiey, E. \u0026amp; Fanimoghadam, H. Chitosan-EDTA-Cellulose network as a green, recyclable and multifunctional biopolymeric organocatalyst for the one-pot synthesis of 2-amino-4H-pyran derivatives. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e12\u003c/strong\u003e, 8642, doi:10.1038/s41598-022-10774-z (2022).\u003c/li\u003e\n\u003cli\u003eDekamin, M. G., Azimoshan, M. \u0026amp; Ramezani, L. Chitosan: a highly efficient renewable and recoverable bio-polymer catalyst for the expeditious synthesis of \u0026alpha;-amino nitriles and imines under mild conditions. \u003cem\u003eGreen Chemistry\u003c/em\u003e \u003cstrong\u003e15\u003c/strong\u003e, 811-820, doi:10.1039/C3GC36901C (2013).\u003c/li\u003e\n\u003cli\u003eDohendou, M., Dekamin, M. G. \u0026amp; Namaki, D. Pd@l-asparagine\u0026ndash;EDTA\u0026ndash;chitosan: a highly effective and reusable bio-based and biodegradable catalyst for the Heck cross-coupling reaction under mild conditions. \u003cem\u003eNanoscale Advances\u003c/em\u003e \u003cstrong\u003e5\u003c/strong\u003e, 2621-2638, doi:10.1039/D3NA00058C (2023).\u003c/li\u003e\n\u003cli\u003eDohendou, M., Dekamin, M. G. \u0026amp; Namaki, D. Supramolecular Pd@methioine-EDTA-chitosan nanocomposite: an effective and recyclable bio-based and eco-friendly catalyst for the green Heck cross-coupling reaction under mild conditions. \u003cem\u003eNanoscale Advances\u003c/em\u003e, doi:10.1039/D3NA00157A (2023).\u003c/li\u003e\n\u003cli\u003eDekamin, M. G.\u003cem\u003e et al.\u003c/em\u003e Alginic acid: A mild and renewable bifunctional heterogeneous biopolymeric organocatalyst for efficient and facile synthesis of polyhydroquinolines. \u003cem\u003eInt J Biol Macromol\u003c/em\u003e \u003cstrong\u003e108\u003c/strong\u003e, 1273-1280, doi:10.1016/j.ijbiomac.2017.11.050 (2018).\u003c/li\u003e\n\u003cli\u003eAlirezvani, Z., Dekamin, M. G., Davoodi, F. \u0026amp; Valiey, E. Melamine-Functionalized Chitosan: A New Bio-Based Reusable Bifunctional Organocatalyst for the Synthesis of Cyanocinnamonitrile Intermediates and Densely Functionalized Nicotinonitrile Derivatives. \u003cem\u003eChemistrySelect\u003c/em\u003e \u003cstrong\u003e3\u003c/strong\u003e, 10450-10463, doi:https://doi.org/10.1002/slct.201802010 (2018).\u003c/li\u003e\n\u003cli\u003eCioc, R. C., Ruijter, E. \u0026amp; Orru, R. V. Multicomponent reactions: advanced tools for sustainable organic synthesis. \u003cem\u003eGreen Chemistry\u003c/em\u003e \u003cstrong\u003e16\u003c/strong\u003e, 2958-2975 (2014).\u003c/li\u003e\n\u003cli\u003eDekamin, M. G.\u003cem\u003e et al.\u003c/em\u003e Alginic acid: a highly efficient renewable and heterogeneous biopolymeric catalyst for one-pot synthesis of the Hantzsch 1, 4-dihydropyridines. \u003cem\u003eRSC Advances\u003c/em\u003e \u003cstrong\u003e4\u003c/strong\u003e, 56658-56664 (2014).\u003c/li\u003e\n\u003cli\u003eDekamin, M. G., Kazemi, E., Karimi, Z., Mohammadalipoor, M. \u0026amp; Naimi-Jamal, M. R. Chitosan: An efficient biomacromolecule support for synergic catalyzing of Hantzsch esters by CuSO4. \u003cem\u003eInternational Journal of Biological Macromolecules\u003c/em\u003e \u003cstrong\u003e93\u003c/strong\u003e, 767-774, doi:https://doi.org/10.1016/j.ijbiomac.2016.09.012 (2016).\u003c/li\u003e\n\u003cli\u003eDekamin, M. G.\u003cem\u003e et al.\u003c/em\u003e Alginic acid: A mild and renewable bifunctional heterogeneous biopolymeric organocatalyst for efficient and facile synthesis of polyhydroquinolines. \u003cem\u003eInternational Journal of Biological Macromolecules\u003c/em\u003e \u003cstrong\u003e108\u003c/strong\u003e, 1273-1280, doi:https://doi.org/10.1016/j.ijbiomac.2017.11.050 (2018).\u003c/li\u003e\n\u003cli\u003eJohn, S. E., Gulati, S. \u0026amp; Shankaraiah, N. Recent advances in multi-component reactions and their mechanistic insights: a triennium review. \u003cem\u003eOrganic Chemistry Frontiers\u003c/em\u003e \u003cstrong\u003e8\u003c/strong\u003e, 4237-4287, doi:10.1039/D0QO01480J (2021).\u003c/li\u003e\n\u003cli\u003eSafapoor, S., Dekamin, M. G., Akbari, A. \u0026amp; Naimi-Jamal, M. R. Synthesis of (E)-2-(1H-tetrazole-5-yl)-3-phenylacrylenenitrile derivatives catalyzed by new ZnO nanoparticles embedded in a thermally stable magnetic periodic mesoporous organosilica under green conditions. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e12\u003c/strong\u003e, 10723, doi:10.1038/s41598-022-13011-9 (2022).\u003c/li\u003e\n\u003cli\u003eRostami, N., Dekamin, M. G., Valiey, E. \u0026amp; FaniMoghadam, H. l-Asparagine\u0026ndash;EDTA\u0026ndash;amide silica-coated MNPs: a highly efficient and nano-ordered multifunctional core\u0026ndash;shell organocatalyst for green synthesis of 3, 4-dihydropyrimidin-2 (1 H)-one compounds. \u003cem\u003eRSC advances\u003c/em\u003e \u003cstrong\u003e12\u003c/strong\u003e, 21742-21759 (2022).\u003c/li\u003e\n\u003cli\u003eShakib, P., Dekamin, M. G., Valiey, E., Karami, S. \u0026amp; Dohendou, M. Ultrasound-Promoted preparation and application of novel bifunctional core/shell Fe3O4@SiO2@PTS-APG as a robust catalyst in the expeditious synthesis of Hantzsch esters. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 8016, doi:10.1038/s41598-023-33990-7 (2023).\u003c/li\u003e\n\u003cli\u003eIshani, M., Dekamin, M. G. \u0026amp; Alirezvani, Z. Superparamagnetic silica core-shell hybrid attached to graphene oxide as a promising recoverable catalyst for expeditious synthesis of TMS-protected cyanohydrins. \u003cem\u003eJournal of Colloid and Interface Science\u003c/em\u003e \u003cstrong\u003e521\u003c/strong\u003e, 232-241, doi:https://doi.org/10.1016/j.jcis.2018.02.060 (2018).\u003c/li\u003e\n\u003cli\u003eFathi, M., Naimi-Jamal, M. R., Dekamin, M. G., Panahi, L. \u0026amp; Demchuk, O. M. A straightforward, environmentally beneficial synthesis of spiro[diindeno[1,2-b:2\u0026prime;,1\u0026prime;-e]pyridine-11,3\u0026prime;-indoline]-2\u0026prime;,10,12-triones mediated by a nano-ordered reusable catalyst. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e11\u003c/strong\u003e, 4820, doi:10.1038/s41598-021-84209-6 (2021).\u003c/li\u003e\n\u003cli\u003eStrecker, A. Ueber die k\u0026uuml;nstliche Bildung der Milchs\u0026auml;ure und einen neuen, dem Glycocoll homologen K\u0026ouml;rper. \u003cem\u003eJustus Liebigs Annalen der Chemie\u003c/em\u003e \u003cstrong\u003e75\u003c/strong\u003e, 27-45 (1850).\u003c/li\u003e\n\u003cli\u003eHantzsch, A. Ueber die synthese pyridinartiger verbindungen aus acetessig\u0026auml;ther und aldehydammoniak. \u003cem\u003eJustus Liebigs Annalen der Chemie\u003c/em\u003e \u003cstrong\u003e215\u003c/strong\u003e, 1-82 (1882).\u003c/li\u003e\n\u003cli\u003eSam, M., Dekamin, M. G. \u0026amp; Alirezvani, Z. Dendrons containing boric acid and 1,3,5-tris(2-hydroxyethyl)isocyanurate covalently attached to silica-coated magnetite for the expeditious synthesis of Hantzsch esters. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e11\u003c/strong\u003e, 2399, doi:10.1038/s41598-020-80884-z (2021).\u003c/li\u003e\n\u003cli\u003eBiginelli, P. \u0026amp; Gazz, P. Synthesis of 3, 4-dihydropyrimidin-2 (1H)-ones. \u003cem\u003eGazz. Chim. Ital\u003c/em\u003e \u003cstrong\u003e23\u003c/strong\u003e, 360-416 (1893).\u003c/li\u003e\n\u003cli\u003eHeravi, M. \u0026amp; Zadsirjan, V. in \u003cem\u003eRecent Advances in Applications of Name Reactions in Multicomponent Reactions\u003c/em\u003e (eds Majid Heravi \u0026amp; Vahideh Zadsirjan) 139-268 (Elsevier, 2020).\u003c/li\u003e\n\u003cli\u003eYaghoubi, A. \u0026amp; Dekamin, M. G. Green and Facile Synthesis of 4H-Pyran Scaffold Catalyzed by Pure Nano-Ordered Periodic Mesoporous Organosilica with Isocyanurate Framework (PMO-ICS). \u003cem\u003eChemistrySelect\u003c/em\u003e \u003cstrong\u003e2\u003c/strong\u003e, 9236-9243, doi:https://doi.org/10.1002/slct.201700717 (2017).\u003c/li\u003e\n\u003cli\u003eBondarian, S., Dekamin, M. G., Valiey, E. \u0026amp; Naimi-Jamal, M. R. Supramolecular Cu(ii) nanoparticles supported on a functionalized chitosan containing urea and thiourea bridges as a recoverable nanocatalyst for efficient synthesis of 1H-tetrazoles. \u003cem\u003eRSC Advances\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 27088-27105, doi:10.1039/D3RA01989F (2023).\u003c/li\u003e\n\u003cli\u003eNikooei, N., Dekamin, M. G. \u0026amp; Valiey, E. Benzene-1, 3, 5-tricarboxylic acid-functionalized MCM-41 as a novel and recoverable hybrid catalyst for expeditious and efficient synthesis of 2, 3-dihydroquinazolin-4 (1 H)-ones via one-pot three-component reaction. \u003cem\u003eResearch on Chemical Intermediates\u003c/em\u003e \u003cstrong\u003e46\u003c/strong\u003e, 3891-3909 (2020).\u003c/li\u003e\n\u003cli\u003eYaghoubi, A., Dekamin, M. G. \u0026amp; Karimi, B. Propylsulfonic Acid-Anchored Isocyanurate-Based Periodic Mesoporous Organosilica (PMO-ICS-PrSO3H): A Highly Efficient and Recoverable Nanoporous Catalyst for the One-Pot Synthesis of Substituted Polyhydroquinolines. \u003cem\u003eCatalysis Letters\u003c/em\u003e \u003cstrong\u003e147\u003c/strong\u003e, 2656-2663, doi:10.1007/s10562-017-2159-5 (2017).\u003c/li\u003e\n\u003cli\u003eAlinasab Amiri, A., Javanshir, S., Dolatkhah, Z. \u0026amp; Dekamin, M. G. SO3H-functionalized mesoporous silica materials as solid acid catalyst for facile and solvent-free synthesis of 2H-indazolo[2,1-b]phthalazine-1,6,11-trione derivatives. \u003cem\u003eNew Journal of Chemistry\u003c/em\u003e \u003cstrong\u003e39\u003c/strong\u003e, 9665-9671, doi:10.1039/C5NJ01733E (2015).\u003c/li\u003e\n\u003cli\u003eDekamin, M. G. \u0026amp; Eslami, M. Highly efficient organocatalytic synthesis of diverse and densely functionalized 2-amino-3-cyano-4H-pyrans under mechanochemical ball milling. \u003cem\u003eGreen Chemistry\u003c/em\u003e \u003cstrong\u003e16\u003c/strong\u003e, 4914-4921, doi:10.1039/C4GC00411F (2014).\u003c/li\u003e\n\u003cli\u003eMachado, I. V., Dos Santos, J. R., Januario, M. A. \u0026amp; Corr\u0026ecirc;a, A. G. Greener organic synthetic methods: Sonochemistry and heterogeneous catalysis promoted multicomponent reactions. \u003cem\u003eUltrasonics Sonochemistry\u003c/em\u003e \u003cstrong\u003e78\u003c/strong\u003e, 105704 (2021).\u003c/li\u003e\n\u003cli\u003eBrand\u0026atilde;o, P., Marques, C. S., Carreiro, E. P., Pineiro, M. \u0026amp; Burke, A. J. Engaging isatins in multicomponent reactions (MCRs)\u0026ndash;easy access to structural diversity. \u003cem\u003eThe Chemical Record\u003c/em\u003e \u003cstrong\u003e21\u003c/strong\u003e, 924-1037 (2021).\u003c/li\u003e\n\u003cli\u003eRimaz, M., Mousavi, H., Ozzar, L. \u0026amp; Khalili, B. Facile, capable, atom-economical one-pot multicomponent strategy for the direct regioselective synthesis of novel isoxazolo [5, 4-d] pyrimidines. \u003cem\u003eResearch on Chemical Intermediates\u003c/em\u003e \u003cstrong\u003e45\u003c/strong\u003e, 2673-2694 (2019).\u003c/li\u003e\n\u003cli\u003eNeochoritis, C. G., Zhao, T. \u0026amp; Dömling, A. Tetrazoles via multicomponent reactions. \u003cem\u003eChemical reviews\u003c/em\u003e \u003cstrong\u003e119\u003c/strong\u003e, 1970-2042 (2019).\u003c/li\u003e\n\u003cli\u003eSunderhaus, J. D., Dockendorff, C. \u0026amp; Martin, S. F. Applications of multicomponent reactions for the synthesis of diverse heterocyclic scaffolds. \u003cem\u003eOrganic letters\u003c/em\u003e \u003cstrong\u003e9\u003c/strong\u003e, 4223-4226 (2007).\u003c/li\u003e\n\u003cli\u003eCores, \u0026Aacute;., Clerigu\u0026eacute;, J., Orocio-Rodr\u0026iacute;guez, E. \u0026amp; Men\u0026eacute;ndez, J. C. Multicomponent reactions for the synthesis of active pharmaceutical ingredients. \u003cem\u003ePharmaceuticals\u003c/em\u003e \u003cstrong\u003e15\u003c/strong\u003e, 1009 (2022).\u003c/li\u003e\n\u003cli\u003eWeber, L. The application of multi-component reactions in drug discovery. \u003cem\u003eCurrent Medicinal Chemistry\u003c/em\u003e \u003cstrong\u003e9\u003c/strong\u003e, 2085-2093 (2002).\u003c/li\u003e\n\u003cli\u003eRuijter, E. \u0026amp; Orru, R. V. Multicomponent reactions\u0026ndash;opportunities for the pharmaceutical industry. \u003cem\u003eDrug Discovery Today: Technologies\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, e15-e20 (2013).\u003c/li\u003e\n\u003cli\u003eMohlala, R. L. \u0026amp; Coyanis, E. M. The vital use of isocyanide-based multicomponent reactions (MCR) in chemical synthesis. \u003cem\u003ePhysical Sciences Reviews\u003c/em\u003e (2023).\u003c/li\u003e\n\u003cli\u003eHossein Nia, R., Taati, Z. \u0026amp; Mamaghani, M. Multi-Component Synthesis of Indole-Substituted Heterocycles\u0026ndash;A Review. \u003cem\u003ePolycyclic Aromatic Compounds\u003c/em\u003e, 1-36 (2023).\u003c/li\u003e\n\u003cli\u003eAlizadeh, M. H., Pooresmaeil, M. \u0026amp; Namazi, H. Carboxymethyl cellulose@multi wall carbon nanotubes functionalized with Ugi reaction as a new curcumin carrier. \u003cem\u003eInternational Journal of Biological Macromolecules\u003c/em\u003e \u003cstrong\u003e234\u003c/strong\u003e, 123778, doi:https://doi.org/10.1016/j.ijbiomac.2023.123778 (2023).\u003c/li\u003e\n\u003cli\u003eOrru, R. V. \u0026amp; Ruijter, E. \u003cem\u003eSynthesis of heterocycles via multicomponent reactions II\u003c/em\u003e. Vol. 2 (Springer Science \u0026amp; Business Media, 2010).\u003c/li\u003e\n\u003cli\u003eZhu, J. \u0026amp; Bienaym\u0026eacute;, H. \u003cem\u003eMulticomponent reactions\u003c/em\u003e. (John Wiley \u0026amp; Sons, 2006).\u003c/li\u003e\n\u003cli\u003eRam\u0026oacute;n, D. J. \u0026amp; Yus, M. Asymmetric multicomponent reactions (AMCRs): the new frontier. \u003cem\u003eAngewandte Chemie International Edition\u003c/em\u003e \u003cstrong\u003e44\u003c/strong\u003e, 1602-1634 (2005).\u003c/li\u003e\n\u003cli\u003eKeivanloo, A., Bakherad, M., Imanifar, E. \u0026amp; Mirzaee, M. Boehmite nanoparticles, an efficient green catalyst for the multi-component synthesis of highly substituted imidazoles. \u003cem\u003eApplied Catalysis A: General\u003c/em\u003e \u003cstrong\u003e467\u003c/strong\u003e, 291-300 (2013).\u003c/li\u003e\n\u003cli\u003eKhazaei, A., Moosavi‐Zare, A. R., Gholami, F. \u0026amp; Khakyzadeh, V. Preparation of 1, 2, 4, 5‐tetrasubstituted imidazoles over magnetic core\u0026ndash;shell titanium dioxide nanoparticles. \u003cem\u003eApplied Organometallic Chemistry\u003c/em\u003e \u003cstrong\u003e30\u003c/strong\u003e, 691-694 (2016).\u003c/li\u003e\n\u003cli\u003eAl Munsur, A. Z., Roy, H. N. \u0026amp; Imon, M. K. Highly efficient and metal-free synthesis of tri-and tetrasubstituted imidazole catalyzed by 3-picolinic acid. \u003cem\u003eArabian Journal of Chemistry\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 8807-8814 (2020).\u003c/li\u003e\n\u003cli\u003eGabla, J. J., Mistry, S. R. \u0026amp; Maheria, K. C. An efficient green protocol for the synthesis of tetra-substituted imidazoles catalyzed by zeolite BEA: effect of surface acidity and polarity of zeolite. \u003cem\u003eCatalysis Science \u0026amp; Technology\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 5154-5167 (2017).\u003c/li\u003e\n\u003cli\u003eNicolaou, K. C., Montagnon, T. \u0026amp; Snyder, S. A. Tandem reactions, cascade sequences, and biomimetic strategies in total synthesis. \u003cem\u003eChem Commun (Camb)\u003c/em\u003e, 551-564, doi:10.1039/b209440c (2003).\u003c/li\u003e\n\u003cli\u003eRotstein, B. H., Zaretsky, S., Rai, V. \u0026amp; Yudin, A. K. Small heterocycles in multicomponent reactions. \u003cem\u003eChemical reviews\u003c/em\u003e \u003cstrong\u003e114\u003c/strong\u003e, 8323-8359 (2014).\u003c/li\u003e\n\u003cli\u003ede Graaff, C., Ruijter, E. \u0026amp; Orru, R. V. Recent developments in asymmetric multicomponent reactions. \u003cem\u003eChemical Society Reviews\u003c/em\u003e \u003cstrong\u003e41\u003c/strong\u003e, 3969-4009 (2012).\u003c/li\u003e\n\u003cli\u003eJiang, B., Rajale, T., Wever, W., Tu, S. J. \u0026amp; Li, G. Multicomponent reactions for the synthesis of heterocycles. \u003cem\u003eChemistry\u0026ndash;An Asian Journal\u003c/em\u003e \u003cstrong\u003e5\u003c/strong\u003e, 2318-2335 (2010).\u003c/li\u003e\n\u003cli\u003eWang, X. B., He, L., Jian, T. Y. \u0026amp; Ye, S. Cyclic phosphoric acid catalyzed one-pot, four-component synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles. \u003cem\u003eChinese Chemical Letters\u003c/em\u003e \u003cstrong\u003e23\u003c/strong\u003e, 13-16 (2012).\u003c/li\u003e\n\u003cli\u003eSilver, M. A. \u0026amp; Albrecht-Schmitt, T. E. Evaluation of f-element borate chemistry. \u003cem\u003eCoordination Chemistry Reviews\u003c/em\u003e \u003cstrong\u003e323\u003c/strong\u003e, 36-51 (2016).\u003c/li\u003e\n\u003cli\u003eLv, L.\u003cem\u003e et al.\u003c/em\u003e Silver‐Catalyzed [3+ 1+ 1] Annulation of Nitrones with Isocyanoacetates as an Approach to 1, 4, 5‐Trisubstituted Imidazoles. \u003cem\u003eEuropean Journal of Organic Chemistry\u003c/em\u003e \u003cstrong\u003e2021\u003c/strong\u003e, 964-968 (2021).\u003c/li\u003e\n\u003cli\u003eBalalaie, S. \u0026amp; Arabanian, A. One-pot synthesis of tetrasubstituted imidazoles catalyzed by zeolite HY and silica gel under microwave irradiation. \u003cem\u003eGreen Chemistry\u003c/em\u003e \u003cstrong\u003e2\u003c/strong\u003e, 274-276 (2000).\u003c/li\u003e\n\u003cli\u003ePerrine, D. M., Ross, J. T., Nervi, S. J. \u0026amp; Zimmerman, R. H. A short, one-pot synthesis of bupropion (Zyban, Wellbutrin). \u003cem\u003eJournal of Chemical Education\u003c/em\u003e \u003cstrong\u003e77\u003c/strong\u003e, 1479 (2000).\u003c/li\u003e\n\u003cli\u003eDai, B.\u003cem\u003e et al.\u003c/em\u003e Iodine catalyzed one-pot multi-component reaction to CF3-containing spiro [indene-2, 3\u0026prime;-piperidine] derivatives. \u003cem\u003eJournal of Fluorine Chemistry\u003c/em\u003e \u003cstrong\u003e133\u003c/strong\u003e, 127-133 (2012).\u003c/li\u003e\n\u003cli\u003eRahman, M., Bagdi, A. K., Kundu, D., Majee, A. \u0026amp; Hajra, A. Zwitterionic‐Type Molten Salt‐Catalyzed Multicomponent Reactions: One‐Pot Synthesis of Substituted Imidazoles Under Solvent‐Free Conditions. \u003cem\u003eJournal of Heterocyclic Chemistry\u003c/em\u003e \u003cstrong\u003e49\u003c/strong\u003e, 1224-1228 (2012).\u003c/li\u003e\n\u003cli\u003eTavakoli, Z., Bagherneghad, M. \u0026amp; Niknam, K. Synthesis of 1, 2, 4, 5‐tetrasubstituted imidazoles using Sulfuric acid ([3‐(3‐Silicapropyl) sulfanyl] propyl] ester as a recyclable solid acid. \u003cem\u003eJournal of Heterocyclic Chemistry\u003c/em\u003e \u003cstrong\u003e49\u003c/strong\u003e, 634-639 (2012).\u003c/li\u003e\n\u003cli\u003eWan, Y.\u003cem\u003e et al.\u003c/em\u003e One‐Pot Synthesis of 1, 2, 4, 5‐Tetrasubstituted Imidazoles in Ionic Liquid. \u003cem\u003eJournal of Heterocyclic Chemistry\u003c/em\u003e \u003cstrong\u003e51\u003c/strong\u003e, 713-718 (2014).\u003c/li\u003e\n\u003cli\u003eLaufer, S. A., Zimmermann, W. \u0026amp; Ruff, K. J. Tetrasubstituted imidazole inhibitors of cytokine release: probing substituents in the N-1 position. \u003cem\u003eJournal of medicinal chemistry\u003c/em\u003e \u003cstrong\u003e47\u003c/strong\u003e, 6311-6325 (2004).\u003c/li\u003e\n\u003cli\u003eHeravi, M. M.\u003cem\u003e et al.\u003c/em\u003e Solvent-free multicomponent reactions using the novel N-sulfonic acid modified poly (styrene-maleic anhydride) as a solid acid catalyst. \u003cem\u003eJournal of Molecular Catalysis A: Chemical\u003c/em\u003e \u003cstrong\u003e392\u003c/strong\u003e, 173-180 (2014).\u003c/li\u003e\n\u003cli\u003eKidwai, M.\u003cem\u003e et al.\u003c/em\u003e One-pot synthesis of highly substituted imidazoles using molecular iodine: A versatile catalyst. \u003cem\u003eJournal of Molecular Catalysis A: Chemical\u003c/em\u003e \u003cstrong\u003e265\u003c/strong\u003e, 177-182 (2007).\u003c/li\u003e\n\u003cli\u003eShaabani, A. \u0026amp; Rahmati, A. Silica sulfuric acid as an efficient and recoverable catalyst for the synthesis of trisubstituted imidazoles. \u003cem\u003eJournal of Molecular Catalysis A: Chemical\u003c/em\u003e \u003cstrong\u003e249\u003c/strong\u003e, 246-248 (2006).\u003c/li\u003e\n\u003cli\u003eTeimouri, A. \u0026amp; Chermahini, A. N. An efficient and one-pot synthesis of 2, 4, 5-trisubstituted and 1, 2, 4, 5-tetrasubstituted imidazoles catalyzed via solid acid nano-catalyst. \u003cem\u003eJournal of Molecular Catalysis A: Chemical\u003c/em\u003e \u003cstrong\u003e346\u003c/strong\u003e, 39-45 (2011).\u003c/li\u003e\n\u003cli\u003eShaterian, H. R. \u0026amp; Ranjbar, M. An environmental friendly approach for the synthesis of highly substituted imidazoles using Br\u0026oslash;nsted acidic ionic liquid, N-methyl-2-pyrrolidonium hydrogen sulfate, as reusable catalyst. \u003cem\u003eJournal of Molecular Liquids\u003c/em\u003e \u003cstrong\u003e160\u003c/strong\u003e, 40-49 (2011).\u003c/li\u003e\n\u003cli\u003eWu, L., Jing, X., Zhu, H., Liu, Y. \u0026amp; Yan, C. One-pot synthesis of polysubstituted imidazoles from arylaldehydes in water catalyzed by NHC using microwave irradiation. \u003cem\u003eJournal of the Chilean Chemical Society\u003c/em\u003e \u003cstrong\u003e57\u003c/strong\u003e, 1204-1207 (2012).\u003c/li\u003e\n\u003cli\u003eKhodaei, M. M., Bahrami, K. \u0026amp; Kavianinia, I. p‐TSA catalyzed synthesis of 2, 4, 5‐triarylimidazoles from ammonium heptamolybdate tetrahydrate in TBAI. \u003cem\u003eJournal of the Chinese Chemical Society\u003c/em\u003e \u003cstrong\u003e54\u003c/strong\u003e, 829-833 (2007).\u003c/li\u003e\n\u003cli\u003eSadeghi, B., Mirjalili, B., Bidaki, S. \u0026amp; Ghasemkhani, M. SbCl5. SiO2: an efficient alternative for one-pot synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles in solvent or under solvent-free condition. \u003cem\u003eJournal of the Iranian Chemical Society\u003c/em\u003e \u003cstrong\u003e8\u003c/strong\u003e, 648-652 (2011).\u003c/li\u003e\n\u003cli\u003eTietze, L. F. \u0026amp; Modi, A. Multicomponent domino reactions for the synthesis of biologically active natural products and drugs. \u003cem\u003eMed Res Rev\u003c/em\u003e \u003cstrong\u003e20\u003c/strong\u003e, 304-322, doi:10.1002/1098-1128(200007)20:4\u0026lt;304::aid-med3\u0026gt;3.0.co;2-8 (2000).\u003c/li\u003e\n\u003cli\u003eBahrami, K., Khodaei, M. M. \u0026amp; Nejati, A. One-pot synthesis of 1, 2, 4, 5-tetrasubstituted and 2, 4, 5-trisubstituted imidazoles by zinc oxide as efficient and reusable catalyst. \u003cem\u003eMonatshefte f\u0026uuml;r Chemie-Chemical Monthly\u003c/em\u003e \u003cstrong\u003e142\u003c/strong\u003e, 159-162 (2011).\u003c/li\u003e\n\u003cli\u003eDas, B., Kashanna, J., Kumar, R. A. \u0026amp; Jangili, P. Synthesis of 2, 4, 5-trisubstituted and 1, 2, 4, 5-tetrasubstituted imidazoles in water using p-dodecylbenzenesulfonic acid as catalyst. \u003cem\u003eMonatshefte f\u0026uuml;r Chemie-Chemical Monthly\u003c/em\u003e \u003cstrong\u003e144\u003c/strong\u003e, 223-226 (2013).\u003c/li\u003e\n\u003cli\u003eHeravi, M. M., Derikvand, F. \u0026amp; Haghighi, M. Highly efficient, four component, one-pot synthesis of tetrasubstituted imidazoles using a catalytic amount of FeCl3\u0026middot; 6H2O. \u003cem\u003eMonatshefte f\u0026uuml;r Chemie-Chemical Monthly\u003c/em\u003e \u003cstrong\u003e139\u003c/strong\u003e, 31-33 (2008).\u003c/li\u003e\n\u003cli\u003ePatil, M. S., Khatri, C. K. \u0026amp; Chaturbhuj, G. U. Three-component, solvent-free synthesis of Betti base catalyzed by sulfated polyborate. \u003cem\u003eMonatshefte f\u0026uuml;r Chemie-Chemical Monthly\u003c/em\u003e \u003cstrong\u003e149\u003c/strong\u003e, 1453-1457 (2018).\u003c/li\u003e\n\u003cli\u003eWu, C.\u003cem\u003e et al.\u003c/em\u003e In situ formation of H-bonding imidazole chains in break-junction experiments. \u003cem\u003eNanoscale\u003c/em\u003e \u003cstrong\u003e12\u003c/strong\u003e, 7914-7920 (2020).\u003c/li\u003e\n\u003cli\u003eValiey, E. \u0026amp; Dekamin, M. G. Pyromellitic diamide\u0026ndash;diacid bridged mesoporous organosilica nanospheres with controllable morphologies: a novel PMO for the facile and expeditious synthesis of imidazole derivatives. \u003cem\u003eNanoscale Advances\u003c/em\u003e \u003cstrong\u003e4\u003c/strong\u003e, 294-308 (2022).\u003c/li\u003e\n\u003cli\u003eZarnegar, Z. \u0026amp; Safari, J. Catalytic activity of Cu nanoparticles supported on Fe 3 O 4\u0026ndash;polyethylene glycol nanocomposites for the synthesis of substituted imidazoles. \u003cem\u003eNew Journal of Chemistry\u003c/em\u003e \u003cstrong\u003e38\u003c/strong\u003e, 4555-4565 (2014).\u003c/li\u003e\n\u003cli\u003eShabalin, D. A. \u0026amp; Camp, J. E. Recent advances in the synthesis of imidazoles. \u003cem\u003eOrg Biomol Chem\u003c/em\u003e \u003cstrong\u003e18\u003c/strong\u003e, 3950-3964, doi:10.1039/d0ob00350f (2020).\u003c/li\u003e\n\u003cli\u003eZhu, Y.\u003cem\u003e et al.\u003c/em\u003e A Facile FeCl3/I2-Catalyzed Aerobic Oxidative Coupling Reaction: Synthesis of Tetrasubstituted Imidazoles from Amidines and Chalcones. \u003cem\u003eOrg Lett\u003c/em\u003e \u003cstrong\u003e17\u003c/strong\u003e, 3872-3875, doi:10.1021/acs.orglett.5b01854 (2015).\u003c/li\u003e\n\u003cli\u003eSparks, R. B. \u0026amp; Combs, A. P. Microwave-Assisted Synthesis of 2, 4, 5-Triaryl-imidazole; A Novel Thermally Induced N-Hydroxyimidazole N\u0026minus; O Bond Cleavage. \u003cem\u003eOrganic letters\u003c/em\u003e \u003cstrong\u003e6\u003c/strong\u003e, 2473-2475 (2004).\u003c/li\u003e\n\u003cli\u003eWolkenberg, S. E.\u003cem\u003e et al.\u003c/em\u003e Efficient synthesis of imidazoles from aldehydes and 1, 2-diketones using microwave irradiation. \u003cem\u003eOrganic Letters\u003c/em\u003e \u003cstrong\u003e6\u003c/strong\u003e, 1453-1456 (2004).\u003c/li\u003e\n\u003cli\u003eMaleki, B., Kahoo, G. E. \u0026amp; Tayebee, R. One-pot synthesis of polysubstituted imidazoles catalyzed by an ionic liquid. \u003cem\u003eOrganic Preparations and Procedures International\u003c/em\u003e \u003cstrong\u003e47\u003c/strong\u003e, 461-472 (2015).\u003c/li\u003e\n\u003cli\u003eZhang, F.\u003cem\u003e et al.\u003c/em\u003e A practical and green approach towards synthesis of multisubstituted imidazoles using boric acid as efficient catalyst. \u003cem\u003ePhosphorus, Sulfur, and Silicon and the Related Elements\u003c/em\u003e \u003cstrong\u003e191\u003c/strong\u003e, 786-789 (2016).\u003c/li\u003e\n\u003cli\u003eTietze, L. F. \u0026amp; Rackelmann, N. Domino reactions in the synthesis of heterocyclic natural products and analogs. \u003cem\u003ePure and Applied Chemistry\u003c/em\u003e \u003cstrong\u003e76\u003c/strong\u003e, 1967-1983, doi:doi:10.1351/pac200476111967 (2004).\u003c/li\u003e\n\u003cli\u003eEsmaeilpour, M., Javidi, J., Dehghani, F. \u0026amp; Zahmatkesh, S. One-pot synthesis of multisubstituted imidazoles catalyzed by Dendrimer-PWAn nanoparticles under solvent-free conditions and ultrasonic irradiation. \u003cem\u003eResearch on Chemical Intermediates\u003c/em\u003e \u003cstrong\u003e43\u003c/strong\u003e, 163-185 (2017).\u003c/li\u003e\n\u003cli\u003eFaniMoghadam, H., Dekamin, M. G. \u0026amp; Rostami, N. Para-Aminobenzoic acid grafted on silica-coated magnetic nanoparticles: a highly efficient and synergistic organocatalyst for on-water synthesis of 2, 3-dihydroquinazolin-4 (1H)-ones. \u003cem\u003eResearch on Chemical Intermediates\u003c/em\u003e \u003cstrong\u003e48\u003c/strong\u003e, 3061-3089 (2022).\u003c/li\u003e\n\u003cli\u003eHanoon, H., Kowsari, E., Abdouss, M., Ghasemi, M. \u0026amp; Zandi, H. Highly efficient and simple protocol for synthesis of 2, 4, 5-triarylimidazole derivatives from benzil using fluorinated graphene oxide as effective and reusable catalyst. \u003cem\u003eResearch on Chemical Intermediates\u003c/em\u003e \u003cstrong\u003e43\u003c/strong\u003e, 4023-4041 (2017).\u003c/li\u003e\n\u003cli\u003eSaghanezhad, S. J., Sayahi, M. H., Imanifar, I., Mombeni, M. \u0026amp; Deris Hamood, S. Caffeine-H3PO4: a novel acidic catalyst for various one-pot multicomponent reactions. \u003cem\u003eResearch on Chemical Intermediates\u003c/em\u003e \u003cstrong\u003e43\u003c/strong\u003e, 6521-6536 (2017).\u003c/li\u003e\n\u003cli\u003eRadinekiyan, F.\u003cem\u003e et al.\u003c/em\u003e A magnetic cross-linked alginate-biobased nanocomposite with anticancer and hyperthermia activities. \u003cem\u003eCarbohydrate Polymer Technologies and Applications\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 100481, doi:https://doi.org/10.1016/j.carpta.2024.100481 (2024).\u003c/li\u003e\n\u003cli\u003eChoopani, L.\u003cem\u003e et al.\u003c/em\u003e Fabrication of a magnetic nanocomposite based on natural hydrogel: Pectin, tragacanth gum, silk fibroin, and integrated graphitic carbon nitride for hyperthermia and biological features. \u003cem\u003eCarbohydrate Polymer Technologies and Applications\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 100495, doi:https://doi.org/10.1016/j.carpta.2024.100495 (2024).\u003c/li\u003e\n\u003cli\u003eChen, L.\u003cem\u003e et al.\u003c/em\u003e Polycarboxylate functionalized magnetic nanoparticles Fe3O4@SiO2@CS-COOH: Preparation, characterization, and immobilization of bovine serum albumin. \u003cem\u003eInternational Journal of Biological Macromolecules\u003c/em\u003e \u003cstrong\u003e260\u003c/strong\u003e, 129617, doi:https://doi.org/10.1016/j.ijbiomac.2024.129617 (2024).\u003c/li\u003e\n\u003cli\u003eBahojb Noruzi, E.\u003cem\u003e et al.\u003c/em\u003e Chemical and physical modification of graphene oxide nano-sheets using casein, Zn-Al layered double hydroxide, alginate hydrogel, and magnetic nanoparticles for biomedical applications. \u003cem\u003eInternational Journal of Biological Macromolecules\u003c/em\u003e \u003cstrong\u003e269\u003c/strong\u003e, 132047, doi:https://doi.org/10.1016/j.ijbiomac.2024.132047 (2024).\u003c/li\u003e\n\u003cli\u003eKarami, N.\u003cem\u003e et al.\u003c/em\u003e Green synthesis of sustainable magnetic nanoparticles Fe3O4 and Fe3O4-chitosan derived from Prosopis farcta biomass extract and their performance in the sorption of lead(II). \u003cem\u003eInternational Journal of Biological Macromolecules\u003c/em\u003e \u003cstrong\u003e254\u003c/strong\u003e, 127663, doi:https://doi.org/10.1016/j.ijbiomac.2023.127663 (2024).\u003c/li\u003e\n\u003cli\u003eMavvaji, M. \u0026amp; Akkoc, S. Recent advances in the application of heterogeneous catalysts for the synthesis of benzimidazole derivatives. \u003cem\u003eCoordination Chemistry Reviews\u003c/em\u003e \u003cstrong\u003e505\u003c/strong\u003e, 215714, doi:https://doi.org/10.1016/j.ccr.2024.215714 (2024).\u003c/li\u003e\n\u003cli\u003eVerma, S. K., Bhadauria, S. S. \u0026amp; Akhtar, S. Review of nondestructive testing methods for condition monitoring of concrete structures. \u003cem\u003eJournal of construction engineering\u003c/em\u003e \u003cstrong\u003e2013\u003c/strong\u003e, 1-11 (2013).\u003c/li\u003e\n\u003cli\u003eThimmaraju, N. \u0026amp; Shamshuddin, S. M. Synthesis of 2, 4, 5-trisubstituted imidazoles, quinoxalines and 1, 5-benzodiazepines over an eco-friendly and highly efficient ZrO 2\u0026ndash;Al 2 O 3 catalyst. \u003cem\u003eRSC advances\u003c/em\u003e \u003cstrong\u003e6\u003c/strong\u003e, 60231-60243 (2016).\u003c/li\u003e\n\u003cli\u003eAkbari, A., Dekamin, M. G., Yaghoubi, A. \u0026amp; Naimi-Jamal, M. R. Novel magnetic propylsulfonic acid-anchored isocyanurate-based periodic mesoporous organosilica (Iron oxide@PMO-ICS-PrSO3H) as a highly efficient and reusable nanoreactor for the sustainable synthesis of imidazopyrimidine derivatives. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 10646, doi:10.1038/s41598-020-67592-4 (2020).\u003c/li\u003e\n\u003cli\u003eRostamnia, S. \u0026amp; Doustkhah, E. Increased SBA-15-SO3H catalytic activity through hydrophilic/hydrophobic fluoroalkyl-chained alcohols (RFOH/SBA-15\u0026ndash;Pr-SO3H). \u003cem\u003eSynlett\u003c/em\u003e \u003cstrong\u003e26\u003c/strong\u003e, 1345-1347 (2015).\u003c/li\u003e\n\u003cli\u003eKumar, T. D. A., Yamini, N., Subrahmanyam, C. \u0026amp; Satyanarayana, K. Design and Optimization of Ecofriendly One-Pot Synthesis of 2, 4, 5-Triaryl-1 H-imidazoles by Three-Component Condensation Using Response Surface Methodology. \u003cem\u003eSynthetic Communications\u003c/em\u003e \u003cstrong\u003e44\u003c/strong\u003e, 2256-2268 (2014).\u003c/li\u003e\n\u003cli\u003eDavoodnia, A., Heravi, M. M., Safavi-Rad, Z. \u0026amp; Tavakoli-Hoseini, N. Green, one-pot, solvent-free synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles using a Br\u0026oslash;nsted acidic ionic liquid as novel and reusable catalyst. \u003cem\u003eSynthetic Communications\u0026reg;\u003c/em\u003e \u003cstrong\u003e40\u003c/strong\u003e, 2588-2597 (2010).\u003c/li\u003e\n\u003cli\u003ePadwa, A. \u0026amp; Bur, S. K. The domino way to heterocycles. \u003cem\u003eTetrahedron\u003c/em\u003e \u003cstrong\u003e63\u003c/strong\u003e, 5341 (2007).\u003c/li\u003e\n\u003cli\u003eSamai, S., Nandi, G. C., Singh, P. \u0026amp; Singh, M. L-Proline: an efficient catalyst for the one-pot synthesis of 2, 4, 5-trisubstituted and 1, 2, 4, 5-tetrasubstituted imidazoles. \u003cem\u003eTetrahedron\u003c/em\u003e \u003cstrong\u003e65\u003c/strong\u003e, 10155-10161 (2009).\u003c/li\u003e\n\u003cli\u003eMukhopadhyay, C., Tapaswi, P. K. \u0026amp; Drew, M. G. Room temperature synthesis of tri-, tetrasubstituted imidazoles and bis-analogues by mercaptopropylsilica (MPS) in aqueous methanol: application to the synthesis of the drug trifenagrel. \u003cem\u003eTetrahedron Letters\u003c/em\u003e \u003cstrong\u003e51\u003c/strong\u003e, 3944-3950 (2010).\u003c/li\u003e\n\u003cli\u003eNiknam, K., Deris, A., Naeimi, F. \u0026amp; Majleci, F. Synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles using silica-bonded propylpiperazine N-sulfamic acid as a recyclable solid acid catalyst. \u003cem\u003eTetrahedron letters\u003c/em\u003e \u003cstrong\u003e52\u003c/strong\u003e, 4642-4645 (2011).\u003c/li\u003e\n\u003cli\u003ePatil, M. S., Palav, A. V., Khatri, C. K. \u0026amp; Chaturbhuj, G. U. Rapid, efficient and solvent-free synthesis of (un) symmetrical xanthenes catalyzed by recyclable sulfated polyborate. \u003cem\u003eTetrahedron Letters\u003c/em\u003e \u003cstrong\u003e58\u003c/strong\u003e, 2859-2864 (2017).\u003c/li\u003e\n\u003cli\u003eRekunge, D. S., Khatri, C. K. \u0026amp; Chaturbhuj, G. U. Sulfated polyborate-catalyzed efficient and expeditious synthesis of (un) symmetrical ureas and benzimidazolones. \u003cem\u003eTetrahedron Letters\u003c/em\u003e \u003cstrong\u003e58\u003c/strong\u003e, 4304-4307 (2017).\u003c/li\u003e\n\u003cli\u003eMalihishoja, A., Dekamin, M. G. \u0026amp; Eslami, M. Magnetic polyborate nanoparticles as a green and efficient catalyst for one-pot four-component synthesis of highly substituted imidazole derivatives. \u003cem\u003eRSC Advances\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 16584-16601, doi:10.1039/D3RA02262E (2023).\u003c/li\u003e\n\u003cli\u003eRossi, R. A., Gaetano; Casotti, Gianluca; Manzini, Chiara, Lessi, Marco. Catalytic Synthesis of 1,2,4,5-Tetrasubstituted 1H-Imidazole Derivatives: State of the Art. \u003cem\u003eAdvanced Synthesis \u0026amp; Catalysis\u003c/em\u003e \u003cstrong\u003e361\u003c/strong\u003e, 2737-2803, doi:10.1002/adsc.201801381 (2019).\u003c/li\u003e\n\u003cli\u003eSadeghi, B., Mirjalili, B. B. F. \u0026amp; Hashemi, M. M. BF3\u0026middot; SiO2: an efficient reagent system for the one-pot synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles. \u003cem\u003eTetrahedron Letters\u003c/em\u003e \u003cstrong\u003e49\u003c/strong\u003e, 2575-2577 (2008).\u003c/li\u003e\n\u003cli\u003eSivakumar, K., Kathirvel, A. \u0026amp; Lalitha, A. Simple and efficient method for the synthesis of highly substituted imidazoles using zeolite-supported reagents. \u003cem\u003eTetrahedron Letters\u003c/em\u003e \u003cstrong\u003e51\u003c/strong\u003e, 3018-3021 (2010).\u003c/li\u003e\n\u003cli\u003eEl hajri, F.\u003cem\u003e et al.\u003c/em\u003e Investigation of catalytic performance of Bis [hydrazinium (1+)] hexafluoridosilicate: (N2H5)2SiF6 in synthesis of 2,4,5-triaryl-1H-imidazoles and 2,3-dihydroquinazolin-4 (1H)-ones under Green conditions. \u003cem\u003eInorganica Chimica Acta\u003c/em\u003e \u003cstrong\u003e536\u003c/strong\u003e, 120915, doi:https://doi.org/10.1016/j.ica.2022.120915 (2022).\u003c/li\u003e\n\u003cli\u003eFattahi, B. \u0026amp; Dekamin, M. G. Fe3O4/SiO2 decorated trimesic acid-melamine nanocomposite: a reusable supramolecular organocatalyst for efficient multicomponent synthesis of imidazole derivatives. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 401, doi:10.1038/s41598-023-27408-7 (2023).\u003c/li\u003e\n\u003cli\u003eSamai, S., Nandi, G. C., Singh, P. \u0026amp; Singh, M. S. l-Proline: an efficient catalyst for the one-pot synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles. \u003cem\u003eTetrahedron\u003c/em\u003e \u003cstrong\u003e65\u003c/strong\u003e, 10155-10161, doi:https://doi.org/10.1016/j.tet.2009.10.019 (2009).\u003c/li\u003e\n\u003cli\u003eKhazaei, A., Nik, H. A. A., Ranjbaran, A. \u0026amp; Moosavi-Zare, A. R. Synthesis, characterization and application of Ni 0.5 Zn 0.5 Fe 2 O 4 nanoparticles for the one pot synthesis of triaryl-1 H-imidazoles. \u003cem\u003eRSC Advances\u003c/em\u003e \u003cstrong\u003e6\u003c/strong\u003e, 78881-78886 (2016).\u003c/li\u003e\n\u003cli\u003eEidi, E., Kassaee, M. Z. \u0026amp; Nasresfahani, Z. Synthesis of 2, 4, 5‐trisubstituted imidazoles over reusable CoFe2O4 nanoparticles: an efficient and green sonochemical process. \u003cem\u003eApplied Organometallic Chemistry\u003c/em\u003e \u003cstrong\u003e30\u003c/strong\u003e, 561-565 (2016).\u003c/li\u003e\n\u003cli\u003eNguyen, T. T., Le, N.-P. T. \u0026amp; Tran, P. H. An efficient multicomponent synthesis of 2, 4, 5-trisubstituted and 1, 2, 4, 5-tetrasubstituted imidazoles catalyzed by a magnetic nanoparticle supported Lewis acidic deep eutectic solvent. \u003cem\u003eRSC Advances\u003c/em\u003e \u003cstrong\u003e9\u003c/strong\u003e, 38148-38153 (2019).\u003c/li\u003e\n\u003cli\u003eGoudarziafshar, H., Moosavi-Zare, A. R. \u0026amp; Jalilian, Z. Synthesis of 2, 4, 5-Tri substituted Imidazoles Using Nano-[Zn-2BSMP] Cl2 as a Schiff Base Complex and Catalyst. \u003cem\u003eOrganic Chemistry Research\u003c/em\u003e \u003cstrong\u003e6\u003c/strong\u003e, 69-81 (2020).\u003c/li\u003e\n\u003cli\u003eSparks, R. B. \u0026amp; Combs, A. P. Microwave-Assisted Synthesis of 2,4,5-Triaryl-imidazole; A Novel Thermally Induced N-Hydroxyimidazole N\u0026minus;O Bond Cleavage. \u003cem\u003eOrganic Letters\u003c/em\u003e \u003cstrong\u003e6\u003c/strong\u003e, 2473-2475, doi:10.1021/ol049124x (2004).\u003c/li\u003e\n\u003cli\u003ePadwa, A. \u0026amp; Bur, S. K. The Domino Way to Heterocycles. \u003cem\u003eTetrahedron\u003c/em\u003e \u003cstrong\u003e63\u003c/strong\u003e, 5341-5378, doi:10.1016/j.tet.2007.03.158 (2007).\u003c/li\u003e\n\u003cli\u003eMoosavi-Zare, A. R., Asgari, Z., Zare, A., Zolfigol, M. A. \u0026amp; Shekouhy, M. One pot synthesis of 1, 2, 4, 5-tetrasubstituted-imidazoles catalyzed by trityl chloride in neutral media. \u003cem\u003eRSC advances\u003c/em\u003e \u003cstrong\u003e4\u003c/strong\u003e, 60636-60639 (2014).\u003c/li\u003e\n\u003cli\u003eAl Munsur, A. Z., Roy, H. N. \u0026amp; Imon, M. K. Highly efficient and metal-free synthesis of tri- and tetrasubstituted imidazole catalyzed by 3-picolinic acid. \u003cem\u003eArabian Journal of Chemistry\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 8807-8814, doi:https://doi.org/10.1016/j.arabjc.2020.10.010 (2020).\u003c/li\u003e\n\u003cli\u003eDai, B.\u003cem\u003e et al.\u003c/em\u003e Iodine catalyzed one-pot multi-component reaction to CF3-containing spiro[indene-2,3\u0026prime;-piperidine] derivatives. \u003cem\u003eJournal of Fluorine Chemistry\u003c/em\u003e \u003cstrong\u003e133\u003c/strong\u003e, 127-133, doi:https://doi.org/10.1016/j.jfluchem.2011.09.006 (2012).\u003c/li\u003e\n\u003cli\u003eNicolaou, K. C., Montagnon, T. \u0026amp; Snyder, S. A. Tandem reactions, cascade sequences, and biomimetic strategies in total synthesis. \u003cem\u003eChemical Communications\u003c/em\u003e, 551-564, doi:10.1039/B209440C (2003).\u003c/li\u003e\n\u003cli\u003eZolfigol, M. A., Baghery, S., Moosavi-Zare, A. R. \u0026amp; Vahdat, S. M. Synthesis of 1,2,4,5-tetrasubstituted imidazoles using 2,6-dimethylpyridinium trinitromethanide {[2,6-DMPyH]C(NO2)3} as a novel nanostructured molten salt and green catalyst. \u003cem\u003eRSC Advances\u003c/em\u003e \u003cstrong\u003e5\u003c/strong\u003e, 32933-32940, doi:10.1039/C5RA03241E (2015).\u003c/li\u003e\n\u003cli\u003eAbdollahi-Alibeik, M. \u0026amp; Moosavifard, M. FeCl3-Doped Polyaniline Nanoparticles as Reusable Heterogeneous Catalyst for the Synthesis of 2-Substituted Benzimidazoles. \u003cem\u003eSynthetic Communications\u003c/em\u003e \u003cstrong\u003e40\u003c/strong\u003e, 2686-2695, doi:10.1080/00397910903318658 (2010).\u003c/li\u003e\n\u003cli\u003eMirjalili, B. F., Bamoniri, A. H. \u0026amp; Zamani, L. One-pot synthesis of 1, 2, 4, 5-tetrasubstituted imidazoles promoted by nano-TiCl4.SiO2. \u003cem\u003eScientia Iranica\u003c/em\u003e \u003cstrong\u003e19\u003c/strong\u003e, 565-568, doi:https://doi.org/10.1016/j.scient.2011.12.013 (2012).\u003c/li\u003e\n\u003cli\u003eNagarapu, L., Apuri, S. \u0026amp; Kantevari, S. Potassium dodecatugstocobaltate trihydrate (K5CoW12O40\u0026middot;3H2O): A mild and efficient reusable catalyst for the one-pot synthesis of 1,2,4,5-tetrasubstituted imidazoles under conventional heating and microwave irradiation. \u003cem\u003eJournal of Molecular Catalysis A: Chemical\u003c/em\u003e \u003cstrong\u003e266\u003c/strong\u003e, 104-108, doi:https://doi.org/10.1016/j.molcata.2006.10.056 (2007).\u003c/li\u003e\n\u003cli\u003eMohammadi Ziarani, G., Dashtianeh, Z., Shakiba Nahad, M. \u0026amp; Badiei, A. One-pot synthesis of 1,2,4,5-tetra substituted imidazoles using sulfonic acid functionalized silica (SiO2-Pr-SO3H). \u003cem\u003eArabian Journal of Chemistry\u003c/em\u003e \u003cstrong\u003e8\u003c/strong\u003e, 692-697, doi:https://doi.org/10.1016/j.arabjc.2013.11.020 (2015).\u003c/li\u003e\n\u003cli\u003eArsalani, N. \u0026amp; Mousavi, S. Z. Synthesis and characterization of water-soluble and carboxy-functional polyester and polyamide based on ethylenediamine-tetraacetic acid and their metal complexes. (2003).\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Table 1 To 3","content":"\u003cp\u003eTable 1 to 3 are available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-4619378/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4619378/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eIn this research, a novel protocol for the synthesis of imidazole derivatives with various substitutions has been investigated in the presence of a new and highly effective magnetic decorated DL-methionine amino acid grafted onto the chitosan backbone by using EDTA linker (CS\u0026thinsp;\u0026minus;\u0026thinsp;EDTA\u0026thinsp;\u0026minus;\u0026thinsp;MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e) under green chemistry conditions. The CS\u0026thinsp;\u0026minus;\u0026thinsp;EDTA\u0026thinsp;\u0026minus;\u0026thinsp;MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanocomposite was properly characterized by using FTIR, EDX, XRD, FESEM, TGA and VSM spectroscopic, microscopic, or analytical methods. The CS\u0026thinsp;\u0026minus;\u0026thinsp;EDTA\u0026thinsp;\u0026minus;\u0026thinsp;MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanocomposite was used as a highly efficient heterogeneous organocatalyst for the synthesis of a wide range of three- and four-substituted imidazole derivatives, as an important pharmaceutical scaffold, through multicomponent reactioins (MCRs) strategy. The CS\u0026thinsp;\u0026minus;\u0026thinsp;EDTA\u0026thinsp;\u0026minus;\u0026thinsp;MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e multifunctional nanocatalyst exhibited high catalytic activity, selectivity, and stability to promote the reactions of benzoin or benzyl, different aldehyde derivatives, and ammonim acetate as well as aromatic or aliphatic amine derivatives in EtOH as green solvent. Key advantages of the present protocol are high to excellent yields, the use of a low loading renewable, bio-based and biodegredable chitosan- as well as amino acid-based nanomaterial, and simple procedure for the preparation of CS\u0026thinsp;\u0026minus;\u0026thinsp;EDTA\u0026thinsp;\u0026minus;\u0026thinsp;MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanomaterial and synthesis of a wide range of imoidazole derivatives. In addition, the catalyst's properties, including its magnetic properties and appropriate surface area characteristicscontribute to its excellent catalytic performance. Fuerthermore, the CS\u0026thinsp;\u0026minus;\u0026thinsp;EDTA\u0026thinsp;\u0026minus;\u0026thinsp;MET@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanocatalyst can be used for up to six cycles for the preparation of imidazole derivatives with only a slight decrease in its catalytic activity.\u003c/p\u003e","manuscriptTitle":"Magnetic DL-methionine grafted to chitosan by EDTA linker nanomaterial: a highly efficient multifunctional organocatalyst for the synthesis of highly substituted imidazole derivatives under green conditions","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-07-18 08:56:43","doi":"10.21203/rs.3.rs-4619378/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"77495113-e457-4ba1-be46-fe8289d8f26d","owner":[],"postedDate":"July 18th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-07-25T08:20:09+00:00","versionOfRecord":[],"versionCreatedAt":"2024-07-18 08:56:43","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4619378","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4619378","identity":"rs-4619378","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}