Sulfamic acid grafted to cross-linked chitosan by dendritic units: a bio-based, highly efficient and heterogeneous organocatalyst for green synthesis of 2,3-dihydroquinazoline derivatives

Abstract

In this work, novel cross-linked chitosan by the G1 dendrimer from condensation of melamine and toluene-2,4-diisocyante terminated by sulfamic acid groups (CS-TDI-Me-TDI-NHSO₃H), as a bio-based and heterogeneous acidic organocatalyst, was designed and prepared. Also, the structure of the prepared organocatalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and thermogravimetric analysis/derivative thermogravimetry (TGA/DTA). Subsequently, the catalytic performance of the biobased and dendritic CS-TDI-Me-TDI-NHSO₃H, as a multifunctional solid acid, was evaluated for the preparation of 2,3-dihydroquinazoline derivatives through a three-component reaction by following green chemistry principles. Some of the advantages of this new protocol include high to excellent yields and short reaction times as well as easy preparation and remarkable catalyst stability of the introduced acidic organocatalyst. The CS-TDI-Me-TDI-SO₃H catalyst can be used for up to five cycles for the preparation of quinazoline derivatives with a slight decrease in its catalytic activity.

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Introduction

Polysaccharide-based scaffolds have been widely used in different fields such as drug delivery, vaccines, wound dressing materials, cosmetics, food additives and packaging, environmental applications including water treatment, and heterogeneous organocatalysts due to their bioactivity, biodegradability and biocompatibility in recent decades.^1–14 Hence, the use of renewable biopolymers such as cellulose, chitin, sodium alginate, and especially chitosan for the design and preparation of efficient biodegradable and heterogeneous organocatalytic systems would be very desirable.^11,15–39 Among these scaffolds, chitosan (CS) is one of the most unique and widely used biopolymers, a natural and active cationic amino polysaccharide obtained from the alkaline N-deacetylation of chitin.^8,24,40–47 Indeed, chitosan has numerous applications in various fields such as preparation of new bio-based materials,^48–52 heterogeneous catalytic systems,^38,53–55 water purification, metal extraction,^56–59 electrolyte-based fuel cells,^60–62 sensors,^6,63 corrosion protection,⁶⁴ etc. However, many research attempts are being made to provide functional chitosan derivatives with chemical modifications. Some of the advantages of using chitosan in various applications include low cost, chemical stability, desirable hydrophilicity, having proper functional groups for chelation of metals, non-toxicity, and environmental friendliness. Compared to homogeneous catalytic systems, heterogeneous ones are much more efficient for multiple and continous use in the chemical synthesis.^65–67 Indeed, heterogeneous catalyst systems benefit from easy removal, recovery and recycling of the catalyst compared to homogeneous catalysts.⁶⁸ Therefore, chitosan application as a new support material for heterogeneous catalysis is increasing.^69,70 Also, the use of ligands containing multi-amine groups in a chain or dendrimer increases the catalytic efficiency by increasing the number of active sites.

Melamine-based dendrimer amines (MDAs) are ideal dendrimer ligands, first reported in 2000 by Simanek and Zhang. MDAs have received a great deal of attention due to the strong binding of amine sites and increasing of the surface hydrophilicity.^71–75 On the other hand, sulfamic acid (H₂NSO₃H) is a common sulfur-containing amino acid with mild acidity, which has been used to replace conventional Lewis and Brønsted acid catalysts.^76–78 Noteworthy, sulfamic acid also exists as H₃N⁺SO₃⁻ zwitterionic units insoluble in non-polar organic solvents. Hence, its catalytic properties arise from its zwitterionic nature and shows excellent activity in acid-catalyzed organic transformations. Thus, it has been widely used, as an acidic catalyst, in reactions such as Michael addition reaction,⁷¹ Pechmann reaction,⁷⁹ Beckmann rearrangement reaction,⁸⁰ imino Diels–Alder reaction,⁸¹ and functional group protection⁸² and deprotection⁸³ reactions.

2,3-Dihydroquinazolines are a group of heterocyclic compounds that have a pyrimidine nucleus in their structure.^84–88 Also, they have received increased attention due to their wide range of biological properties such as anesthetic,⁸⁹ anti-cancer,⁹⁰ muscle relaxant⁹¹ and sedative properties.⁹² Therefore, synthesis of 2,3-dihydroquinazoline derivatives has attracted the attention of organic and pharmaceutical chemists, leading to various methods for the preparation of 2,3-dihydroquinazoline derivatives in order to achieve higher reaction efficiency.^70,93–105 Most of these reported methods have disadvantages such as multi-stage preparation methods, long reaction time, low efficiency, hard reaction conditions, and the use of precious metals or toxic reagents. Thus, using new methods for the synthesis of 2,3-dihydroquinazolines under desired reaction conditions is important.

In the present work, sulfamic acid grafted to cross-linked chitosan by dendritic units (CS-TDI-Me-TDI-NHSO₃H, 1) organocatalyst was designed, prepared and characterized. The CS-TDI-Me-TDI-NHSO₃H was used as a heterogeneous and green nanocatalyst for the synthesis of 2,3-dihydroquinazoline derivatives (Scheme 1).

Scheme 1 CS-TDI-Me-TDI-NHSO₃H (1), as solid acid catalyst, for green synthesis of 2,3-dihydroquinazoline derivatives by using aldehyde derivatives (2), isatoic anhydride (3) and ammonium acetate (4) in EtOH under reflux conditions.

Results and discussion

The prepared CS-TDI-Me-TDI-HNSO₃H organocatalyst (1) was characterized using various suitable techniques including FT-IR, FESEM, XRD, TGA and EDS.

Fig. 1 shows the FT-IR spectra of melamine–toluene 2,4-diisocyanate intermediate (I, a) and CS-TDI-Me-TDI-HNSO₃H (1, b). According to Fig. 1a, the absorption bands at 3468–3334 cm⁻¹ are attributed to the stretching vibration of N–H bonds of amin groups. Also, absorption band at 2926 cm⁻¹ belongs to the stretching vibration of C–H aliphatic bonds. In addition, the adsorption bands at 2276 cm⁻¹ and 1652 cm⁻¹ correspond to the vibration of N=C=O and C=O bonds of the amide. As shown in Fig. 1b, the absorption bands at 3470–3336 cm⁻¹ are attributed to the stretching vibration of N–H bonds of the amine groups. Also, the absorption band at 2976 cm⁻¹ belongs to the stretching vibration of C–H aliphatic bonds. Whereas, the adsorption band at 1654 cm⁻¹ is related to the stretching vibration of C=O bond of amide groups. Also, the characteristic bands at 1208 cm⁻¹ and 1026 cm⁻¹ correspond to the asymmetric and symmetric S=O stretching vibration in the SO₃H group, respectively.

Fig. 1 FTIR spectra of melamine–toluene 2,4-diisocyanate intermediate (I, a) and CS-TDI-Me-TDI-HNSO₃H bio-based material (1, b).

Fig. 2 shows the XRD pattern of CS-TDI-Me-TDI-HNSO₃H (1). There are symmetrical reflections at 2θ of 17.56°, 21.52°, 26.08°, 28.71°, and 29.72° which are characteristic of the CS-TDI-Me-TDI-HNSO₃H (1) structure according to the standard XRD patterns of melamine (JCPDS card no. 00-039-1950), chitosan (JCPDS card no. 00-040-1518), and H₂NSO₃H (JCPDS card no. 01-070-0060). As can be seen, the results obtained from the XRD pattern of CS-TDI-Me-TDI-HNSO₃H (1) confirm the successful preparation of the desired nanomaterial.

Fig. 2 Wide-angle XRD pattern of CS-TDI-Me-TDI-HNSO₃H nanomaterial (1).

Fig. 3 shows the EDS analysis related to the CS-TDI-Me-TDI-HNSO₃H organocatlyst (1), which confirms the presence of C, O, N, and S elements in its structure. Therefore, the presence of S element indicates the grafting of H₂NSO₃H on the chitosan backbone. Also, EDS mapping analysis shows uniform particle distribution of the structure.

Fig. 3 EDS spectra of the CS-TDI-Me-TDI-HNSO₃H organocatalyst (1).

FESEM images of CS-TDI-Me-TDI-HNSO₃H (1) nanomaterial (1) are shown in Fig. 4. FESEM images of structure of CS-TDI-Me-TDI-HNSO₃H shows that the morphology of chitosan has changed from sheets to irregular particles, which confirms the formation of the desired structure. Also, these particles have a uniform dispersion and average particle size of 25–44 nm.

Fig. 4 FESEM images of CS-TDI-Me-TDI-HNSO₃H nanomaterial (1).

Using thermogravimetric analysis (TGA), the thermal stability of the prepared catalyst (1) was investigated in the temperature range of 50–500 °C. As shown in Fig. 5, two weight loss steps were observed between 270 and 400 °C, Since the pristine chitosan is degraded at 200–220°,¹⁰⁶ this degradation at the temperature range of 270–400 °C indicates that the organic units on the surface of chitosan have been linked by toluene diisocyanate, which affects the thermal stability of chitosan and degradation takes place at a higher temperature.

Fig. 5 TGA curves of CS-TDI-Me-TDI-HNSO₃H organocatalyst (1).

Optimization of conditions for the synthesis of 2,3-dihydroquinazoline derivatives in the presence of CS-TDI-Me-TDI-HNSO₃H organocatalyst (1)

In this section, the efficacy of CS-TDI-Me-TDI-HNSO₃H nanomaterial (1) in the model reaction for the synthesis of 2, 3-dihydroquinazoline derivatives was investigated. 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 investigated in the presence of 4-chloroaldehyde (2a, 0.5 mmol), isatoic anhydride (3, 0.5 mmol) and ammonium acetate (4, 1.5 mmol) for the synthesis of 2,3-dihydroquinazoline derivatives in various conditions. First, the model reaction was run without catalyst using various solvents at different temperatures (Table 1, entries 1–4). As shown in Table 1, without catalyst, the model reaction did not proceed to afford the desired product after 1 h. However, in the presence of 15 mg of CS-TDI-Me-TDI-HNSO₃H organocatalyst (1), the desired product 5a was prepared in medium to excellent yields (57 to 97%, Table 1, entries 5–8). The progress of the model reaction to afford the desired product 5a in EtOH was investigated at temperatures rather than reflux conditions (Table 1, entries 9 and 10). Based on the obtained results, EtOH under reflux conditions can be considered as the desirable solvent. Afterward, to determine the desirable amount of catalyst, the model reaction was carried out in EtOH under reflux conditions in the presence of 10, 15 and 20 mg of CS-TDI-Me-TDI-HNSO₃H organocatalyst (1) (Table 1, entries 10–12). Consequently, 15 mg of CS-TDI-Me-TDI-HNSO₃H organocatalyst (1) loading in EtOH under reflux conditions were selected as the optimal reaction conditions.

Table 1 Screening of optimized conditions for three component reaction of 4-chloroaldehyde (2a), isatoic anhydride (3) and ammonium acetate (4) to afford 2,3-dihydroquinazoline derivative 5a in the presence of CS-TDI-Me-TDI-HNSO₃H solid acid (1)^a

Entry	Catalyst	Conditions	Catalyst loading (mg)	Time (min)	Yield (%)
a Reaction conditions: 4-chloroaldehyde (2a, 0.5 mmol), isatoic anhydride (3, 0.5 mmol) and ammonium acetate (4, 1.5 mmol) in the presence of CS-TDI-Me-TDI-HNSO3H (1) unless otherwise noted.
1	—	EtOH/RT	—	60	Trace
2	—	CH2Cl2/RT	—	60	—
3	—	H2O/RT	—	60	—
4	—	DMF/RT	—	60	Trace
5	CS-TDI-Me-TDI-HNSO3H (1)	EtOH/reflux	15	15	97
6	CS-TDI-Me-TDI-HNSO3H (1)	H2O/reflux	15	60	57
7	CS-TDI-Me-TDI-HNSO3H (1)	CH2Cl2/reflux	15	60	40
8	CS-TDI-Me-TDI-HNSO3H (1)	DMF/reflux	15	60	62
9	CS-TDI-Me-TDI-HNSO3H (1)	EtOH/RT	15	40	50
10	CS-TDI-Me-TDI-HNSO3H (1)	EtOH/50 °C	15	20	87
11	CS-TDI-Me-TDI-HNSO3H (1)	EtOH/reflux	10	15	80
12	CS-TDI-Me-TDI-HNSO3H (1)	EtOH/reflux	20	45	83

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After that, in order to extend the catalytic application of CS-TDI-Me-TDI-HNSO₃H (1), three-component condensation of aldehyde derivatives (2a–m, 0.5 mmol), isatoic anhydride (3, 0.5 mmol), and ammonium acetate (4, 1.5 mmol) was performed under optimal conditions for the synthesis of 2,3-dihydroquinazoline derivatives (5a–m). The results are summarized in Table 2.

Table 2 Synthesis of 2,3-dihydroquinazoline derivatives (5a–m) through the three-component condensation of aldehyde derivatives (2a–m), isatoic anhydride (3), and ammonium acetate (4) in the presence of CS-TDI-Me-TDI-HNSO₃H organocatalyst (1)^a

Entry	Aldehyde	Product	Time (min)	Yield (%)	M.p. (°C) (Obs.)	M.p. (°C) (Lit.)
a Reaction conditions: aldehyde derivatives (2a–m, 0.5 mmol), isatoic anhydride (3, 0.5 mmol) and ammonium acetate (4, 1.5 mmol) in the presence of CS-TDI-Me-TDI-HNSO3H (1, 15 mg) in EtOH under reflux conditions.
1			15	97	204–206	203–206 (ref. 107)
2			15	95	207–209	206–208 (ref. 108)
3			25	87	198–201	200–202 (ref. 107)
4			55	80	190–192	190–193 (ref. 107)
5			25	87	194–195	193–197 (ref. 109)
6			25	86	197–199	196–198 (ref. 109)
7			15	90	165–169	166–169 (ref. 107)
8			20	90	209–211	208–210 (ref. 109)
9			30	89	199–202	198–201 (ref. 110)
10			45	90	179–181	178–182 (ref. 87)
11			25	86	214–217	213–215 (ref. 109)
12			35	92	350–352	351–352 (ref. 87)
13			40	91	166–168	165–167 (ref. 111)

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The possible mechanism for the synthesis of 2,3-dihydroquinazoline derivatives in the presence of CS-TDI-Me-TDI-HNSO₃H (1)

Scheme 2 shows the proposed mechanism for the synthesis of 2,3-dihydroquinazoline derivatives. CS-TDI-Me-TDI-HNSO₃H organocatalyst (1) has Brønsted acidic centers. Hence, it activates carbonyl groups in isotonic anhydride by forming a hydrogen bond to facilitate the nucleophilic addition of ammonium acetate (4) and forming the intermediate I. Next, this intermediate reacts with aldehyde derivatives and forms intermediate II. Finally, by removing H₂O from intermediate II, 2,3-dihydroquinazoline derivatives 5 are synthesized as the desired product.

Scheme 2 The proposed mechanism for the synthesis of 2,3-dihydroquinazoline derivatives 5 catalyzed by the biobased multifunctional CS-TDI-Me-TDI-HNSO₃H solid acid (1).

Also, the reusability of CS-TDI-Me-TDI-HNSO₃H solid acid catalyst (1) was studied in the synthesis of 2,3-dihydroquinazoline derivative 5a. For this purpose, the CS-TDI-Me-TDI-HNSO₃H (1) was separated by filtration, washed with water and acetone, and then dried at 70 °C for 24 h. The recycled organocatalyst in each run was used after activation for the preparation of 2,3-dihydroquinazoline derivative 5a in the next run. This reaction was repeated up to five times and no significant reduction was observed in the CS-TDI-Me-TDI-HNSO₃H organocatalyst (1) efficiency (Fig. 6).

Fig. 6 Reusability of the CS-TDI-Me-TDI-HNSO₃H organocatalyst (1) in the model reaction to afford 5a.

Table 3 compares the efficiency of dendritic CS-TDI-Me-TDI-HNSO₃H organocatalyst (1) with other catalysts for the synthesis of desired 2,3-dihydroquinazoline derivative 5a. For this comparison, several parameters, e.g., the reaction time, temperature, and the reaction yield, were taken into consideration. It can be seen that CS-TDI-Me-TDI-HNSO₃H heterogeneous catalyst (1) showed higher efficiency than previously reported catalysts for the synthesis of 2,3-dihydroquinazoline derivatives.

Table 3 Comparison of the catalytic efficiency of CS-TDI-Me-TDI-HNSO₃H (1) with other heterogeneous catalysts for 4-cholorobenzaldhyde

Entry	Catalyst	Time (min)	Solvent/temperature conditions	Yield (%)	Reference
1	CS-TDI-Me-TDI-HNSO3H (1)	15	EtOH/reflux	97	This work
2	Wang-OSO3H	40	H2O/100 °C	84	108
3	Titanium silicon oxide nanopowder	120	H2O/100 °C	94	112
4	Montmorillonite-KSF	150	Solvent-free/100 °C	93	113
5	Al(H2PO4)3	540	Solvent-free/100 °C	70	114
6	Co-aminobenzamid@Al-SBA-15	24	EtOH/reflux	96	115

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Experimental

Materials and methods

The CS-TDI-Me-TDI-HNSO₃H nanomaterial (1) was purely prepared by modifing of known methods for similar materials having the same functional groups. Chitosan (CS, MW = 100 000–300 000 Da) was obtained from Acros Organics. Melamine (Me) and triethylamine (TEA) were provided by Sigma-Aldrich. Tetrahydrofuran (THF), sulfamic acid (H₂NSO₃H), and toluene-2,4-diisocyanate (TDI) were purchased from Merck-Millipore. Other chemical compounds were supplied by Merck and Aldrich Chemical Co. Characterization of the heterogeneous CS-TDI-Me-TDI-H₂NSO₃H (1) organocatalyst was performed using FESEM (TESCAN-MIRA III), EDS (TESCAN-MIRA II), TGA (STA 504, Bahr Co.), and XRD (Bourevestnik DRON-8) analyses. ¹H NMR (500 MHz) spectra recorded on a Bruker DRX-500 Avance spectrometers in DMSO, as the solvent, at ambient temperature. FT-IR spectra were recorded as KBr pellets on a Shimadzu FT-IR-8400S spectrometer. Analytical thin-layer chromatography (TLC) was performed using Merck 0.2 mm silica gel 60F-254 Al-plates for reaction monitoring. Melting points were determined using an Electrothermal 9100 apparatus.

General method for preparation of CS-TDI-Me-TDI-HNSO₃H organocatalyst (1). To a round button flask, a mixture of melamine (4 mmol, 0.5 g), TDI (12 mmol, 2 mL) and THF (15 mL) was added and stirred at room temperature under nitrogen atmosphere for 24 h. The obtained white solid (I) was filtered off and washed with THF, then dried in a vacuum oven at 60 °C for 12 h (Scheme 3). Also, H₃N⁺SO₃⁻ (8 mmol, 0.776 g) and TEA (10 mmol, 1.4 mL) were added to THF (5 mL) and stirred for 2 h. Subsequently, the white solid (I) was added to the mixture and stirred for another 24 h at room temperature. Then, CS (0.5 g) was added and refluxed for 24 h under nitrogen atmosphere. Finally, the obtained white powder was filtered and washed with THF and EtOH and dried at 60 °C for 24 h (Scheme 3).

Scheme 3 Schematic representation of CS-TDI-Me-TDI-HNSO₃H (1) preparation steps.

General procedure for the synthesis of 2,3-dihydroquinazoline derivatives. A mixture of aldehyde derivatives (2, 0.5 mmol), isatoic anhydride (3, 0.5 mmol), ammonium acetate (4, 1.5 mmol), CS-TDI-Me-TDI- HNSO₃H (1, 15 mg), and EtOH (5 mL) was stirred at 80 °C. After completion of the reaction, the organocatalyst was filtered and washed with acetone. The products were purified by recrystallization from EtOH. The products were identified by melting point measurement, FT-IR and ¹HNMR spectroscopy.

Selected spectral data.
2-(4-Chlorophenyl)-2,3-dihydroquinazolin-4(1H)-one (2a). Melting point: 212–214 °C; FTIR (KBr, cm⁻¹): 3305, 3184, 3062, 1654, 1606, 1431, 1090, 749 cm⁻¹. ¹H NMR (500 MHz, DMSO-d₆): δ_H (ppm) = 5.77 (s, 1H, CH), 6.68 (t, 1H, Ar–H), 6.74 (d, 1H, Ar–H), 7.10 (s, 1H, NH), 7.24 (t, 1H, Ar–H), 7.45 (d, 1H, Ar–H), 7.50 (d, 1H, Ar–H), 7.61 (d, 1H, Ar–H), 8.27 (s, 1H, CONH).
2-(2-Chlorophenyl)-2,3-dihydroquinazolin-4(1H)-one (5b). Melting point: 207–209 °C; FTIR (cm⁻¹): 3310, 3207, 3050, 1660, 1492, 1479; ¹H NMR (500 MHz, DMSO-d₆): δ_H (ppm) 6.14 (s, 1H), 6.72 (t, 1H, J = 7.5 Hz), 6.77 (d, 1H, J = 8.1 Hz), 7.01 (s, 1H), 7.26 (t, 1H, J = 7.7 Hz), 7.40 (d, 2H, J = 4.1 Hz), 7.49 (d, 1H, J = 4.1 Hz), 7.66 (d, 2H, J = 6.7, Hz), 8.21 (s, 1H).
2-(4-Methylphenyl)-2,3-dihydroquinazolin-4(1H)-one (5i). Melting point: 199–202 °C; FTIR (cm⁻¹): 3300, 3170, 3032, 2931, 2827, 1510, 1249; ¹H NMR (500 MHz, DMSO-d₆): δ_H (ppm) 2.29 (s, 3H), 5.70 (s, 1H), 6.66 (t, 1H, J = 7.4 Hz), 6.73 (d, 1H, J = 8.1 Hz), 7.04 (s, 1H), 7.19 (d, J = 7.6 Hz, 1H), 7.23 (t, J = 8.1 Hz, 1H), 7.37 (d, J = 7.8 Hz, 2H), 7.61 (d, J = 7.6 Hz, 1H), 8.22 (s, 1H); δ_C (ppm) ¹³C NMR (125 MHz, DMSO-d₆): 162.70, 152.90, 141.98, 134.99, 130.28, 129.65, 128.21, 127.64, 127.58, 126.88, 126.30, 121.23, 21.23.
2-(4-Methoxylphenyl)-2,3-dihydroquinazolin-4(1H)-one (5j). Melting point: 179–181 °C; FTIR (cm⁻¹): 3301, 3170, 3029, 2930, 2825, 1511, 1248; ¹H NMR (500 MHz, DMSO-d₆): δ_H (ppm) 3.74 (s, 3H), 5.70 (s, 1H), 6.67 (t, 1H, J = 7.6 Hz), 6.74 (d, 1H, J = 8.1 Hz), 6.95 (d, 2H, J = 8.4), 7.00 (s, 1H), 7.23 (t, J = 8.0 Hz, 1H), 7.42 (d, J = 7.6 Hz, 2H), 7.61 (d, J = 7.6 Hz, 1H), 8.17 (s, 1H); ¹³C NMR (125 MHz, DMSO-d₆): δ_C (ppm) 162.62, 152.84, 135.49, 135.14, 130.07, 126.94, 126.79, 126.37, 124.56, 120.92, 118.30, 114.36, 55.74.

Conclusions

In this paper, a new heterogeneous acidic catalyst based on the renewable and biodegradable chitosan polymer, i.e., CS-TDI-Me-TDI-HNSO₃H, was prepared and characterized using various spectral and analytical techniques. Subsequently, CS-TDI-Me-TDI-HNSO₃H was used, as a solid acid, for the synthesis of 2,3-dihydroquinazoline derivatives under green conditions. The desired 2,3-dihydroquinazoline derivatives were prepared in high to excellent yields under optimal conditions. Low catalyst loading, mild reaction conditions and very short reaction times as well as reusability of the catalyst for at least four consecutive catalytic cycles without significant loss of its activity are the advantages of this new protocol.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

We are grateful for the financial support from The Research Council of Iran University of Science and Technology (IUST), Tehran, Iran (Grant No. 160/20969). We would also like to acknowledge the support of the Iran Nanotechnology Initiative Council (INIC).

References

1. M. N. R. Kumar, React. Funct. Polym., 2000, 46, 1–27.
2. J. Dinoro, M. Maher, S. Talebian, M. Jafarkhani, M. Mehrali, G. Orive, J. Foroughi, M. S. Lord and A. Dolatshahi-Pirouz, Biomaterials, 2019, 214, 119214.
3. R. F. B. de Souza, F. C. B. de Souza, C. Rodrigues, B. Drouin, K. C. Popat, D. Mantovani and Â. M. Moraes, Mater. Sci. Eng., C, 2019, 94, 364–375.
4. A. Barbetta, A. Carrino, M. Costantini and M. Dentini, Soft Matter, 2010, 6, 5213–5224.
5. Y. Cohen, R. Rutenberg, G. Cohen, B. Veltman, R. Gvirtz, E. Fallik, D. Danino, E. Eltzov and E. Poverenov, ACS Appl. Bio Mater., 2020, 3, 2209–2217.
6. C. Cui, Q. Fu, L. Meng, S. Hao, R. Dai and J. Yang, ACS Appl. Bio Mater., 2021, 4, 85–121.
7. L. Xu, Z. Chu, H. Wang, L. Cai, Z. Tu, H. Liu, C. Zhu, H. Shi, D. Pan, J. Pan and X. Fei, ACS Appl. Bio Mater., 2019, 2, 3429–3438.
8. B. Zhao, C. Lou, Q. Zhou, Y. Zhu, W. Li and M. Jingshan, RSC Adv., 2022, 12, 8256–8262.
9. R. A. Muzzarelli, J. Boudrant, D. Meyer, N. Manno, M. DeMarchis and M. G. Paoletti, Carbohydr. Polym., 2012, 87, 995–1012.
10. M. G. Dekamin, E. Kazemi, Z. Karimi, M. Mohammadalipoor and M. R. Naimi-Jamal, Int. J. Biol. Macromol., 2016, 93, 767–774.
11. H. Hamedi, S. Moradi, S. M. Hudson, A. E. Tonelli and M. W. King, Carbohydr. Polym., 2022, 119100.
12. S. Torkaman, H. Rahmani, A. Ashori and S. H. M. Najafi, Carbohydr. Polym., 2021, 258, 117675.
13. N. Rostami, M. G. Dekamin, E. Valiey and H. FaniMoghadam, RSC Adv., 2022, 12, 21742–21759.
14. X. Chen, H. Yang and N. Yan, Chem.–Eur. J., 2016, 22, 13402–13421.
15. A. El Kadib, ChemSusChem, 2015, 8, 217–244.
16. B. List, R. A. Lerner and C. F. Barbas, J. Am. Chem. Soc., 2000, 122, 2395–2396.
17. D. W. C. MacMillan, Nature, 2008, 455, 304–308.
18. A. Antenucci, S. Dughera and P. Renzi, ChemSusChem, 2021, 14, 2785–2853.
19. M. Debruyne, V. Van Speybroeck, P. Van Der Voort and C. V. Stevens, Green Chem., 2021, 23, 7361–7434.
20. F. Khan and S. R. Ahmad, Macromol. Biosci., 2013, 13, 395–421.
21. S. K. L. Levengood and M. Zhang, J. Mater. Chem. B, 2014, 2, 3161–3184.
22. J. Wróblewska-Krepsztul, T. Rydzkowski, I. Michalska-Pożoga and V. K. Thakur, Nanomaterials, 2019, 9, 404.
23. M. Lee, B.-Y. Chen and W. Den, Appl. Sci., 2015, 5, 1272–1283.
24. M. U. A. Khan, S. Haider, M. A. Raza, S. A. Shah, S. I. Abd Razak, M. R. A. Kadir, F. Subhan and A. Haider, Int. J. Biol. Macromol., 2021, 192, 820–831.
25. F. Li, S. Y. H. Abdalkarim, H.-Y. Yu, J. Zhu, Y. Zhou and Y. Guan, ACS Appl. Bio Mater., 2020, 3, 1944–1954.
26. S. Mukherjee, J. W. Yang, S. Hoffmann and B. List, Chem. Rev., 2007, 107, 5471–5569.
27. J. Alkabli, M. A. Rizk, R. F. Elshaarawy and W. El-Sayed, Int. J. Biol. Macromol., 2021, 184, 454–462.
28. Z. Kheilkordi, G. Mohammadi Ziarani, F. mohajer, A. Badiei and M. Sillanpää, RSC Adv., 2022, 12, 12672–12701.
29. N. Rostami, M. G. Dekamin, E. Valiey and H. Fanimoghadam, Sci. Rep., 2022, 12, 8642.
30. Z. Alirezvani, M. G. Dekamin and E. Valiey, Sci. Rep., 2019, 9, 17758.
31. E. Valiey, M. G. Dekamin and Z. Alirezvani, Int. J. Biol. Macromol., 2019, 129, 407–421.
32. Z. Alirezvani, M. G. Dekamin, F. Davoodi and E. Valiey, ChemistrySelect, 2018, 3, 10450–10463.
33. M. G. Dekamin, S. Z. Peyman, Z. Karimi, S. Javanshir, M. R. Naimi-Jamal and M. Barikani, Int. J. Biol. Macromol., 2016, 87, 172–179.
34. M. G. Dekamin, Z. Karimi, Z. Latifidoost, S. Ilkhanizadeh, H. Daemi, M. R. Naimi-Jamal and M. Barikani, Int. J. Biol. Macromol., 2018, 108, 1273–1280.
35. M. G. Dekamin, S. Ilkhanizadeh, Z. Latifidoost, H. Daemi, Z. Karimi and M. Barikani, RSC Adv., 2014, 4, 56658–56664.
36. G. Rajesh Krishnan and K. Sreekumar, in New and Future Developments in Catalysis, ed. S. L. Suib, Elsevier, Amsterdam, 2013, pp. 343–364,  DOI:10.1016/B978-0-444-53876-5.00016-7.
37. S. Ilkhanizadeh, J. Khalafy and M. G. Dekamin, Int. J. Biol. Macromol., 2019, 140, 605–613.
38. M. G. Dekamin, M. Azimoshan and L. Ramezani, Green Chem., 2013, 15, 811–820.
39. X. Chen, S. Song, H. Li, G. k. Gözaydın and N. Yan, Acc. Chem. Res., 2021, 54, 1711–1722.
40. V. Mourya and N. N. Inamdar, React. Funct. Polym., 2008, 68, 1013–1051.
41. X. Fei Liu, Y. Lin Guan, D. Zhi Yang, Z. Li and K. De Yao, J. Appl. Polym. Sci., 2001, 79, 1324–1335.
42. M. R. Kumar, R. A. Muzzarelli, C. Muzzarelli, H. Sashiwa and A. Domb, Chem. Rev., 2004, 104, 6017–6084.
43. Q. Li, E. Dunn, E. Grandmaison and M. F. Goosen, J. Bioact. Compat. Polym., 1992, 7, 370–397.
44. T. Chandy and C. P. Sharma, Biomater., Artif. Cells, Artif. Organs, 1990, 18, 1–24.
45. A. M. Heimbuck, T. R. Priddy-Arrington, M. L. Padgett, C. B. Llamas, H. H. Barnett, B. A. Bunnell and M. E. Caldorera-Moore, ACS Appl. Bio Mater., 2019, 2, 2879–2888.
46. J. Zhu, G. Jiang, G. Song, T. Liu, C. Cao, Y. Yang, Y. Zhang and W. Hong, ACS Appl. Bio Mater., 2019, 2, 5042–5052.
47. L.-Y. Zheng and J.-F. Zhu, Carbohydr. Polym., 2003, 54, 527–530.
48. J. Zhou, Z. Dong, H. Yang, Z. Shi, X. Zhou and R. Li, Appl. Surf. Sci., 2013, 279, 360–366.
49. P. K. Sahu, P. K. Sahu, S. K. Gupta and D. D. Agarwal, Ind. Eng. Chem. Res., 2014, 53, 2085–2091.
50. E. Guibal, Prog. Polym. Sci., 2005, 30, 71–109.
51. F. Quignard, A. Choplin and A. Domard, Langmuir, 2000, 16, 9106–9108.
52. X. Zhao, S. Li, Y. Hu, X. Zhang, L. Chen, C. Wang, L. Ma and Q. Zhang, Chem. Eng. J., 2022, 428, 131368.
53. N. Sudheesh, S. K. Sharma and R. S. Shukla, J. Mol. Catal. A: Chem., 2010, 321, 77–82.
54. M. Dohendou, K. Pakzad, Z. Nezafat, M. Nasrollahzadeh and M. G. Dekamin, Int. J. Biol. Macromol., 2021, 192, 771–819.
55. Z. Kheilkordi, G. M. Ziarani, F. Mohajer, A. Badiei and R. S. Varma, Green Chem., 2022, 24, 4304–4327.
56. V. Mohanasrinivasan, M. Mishra, J. S. Paliwal, S. K. Singh, E. Selvarajan, V. Suganthi and C. Subathra Devi, 3 Biotech, 2014, 4, 167–175.
57. N. Li and R. Bai, Water Sci. Technol., 2006, 54, 103–113.
58. M. Barakat, Arabian J. Chem., 2011, 4, 361–377.
59. M. Sivakami, T. Gomathi, J. Venkatesan, H.-S. Jeong, S.-K. Kim and P. Sudha, Int. J. Biol. Macromol., 2013, 57, 204–212.
60. J. Ma and Y. Sahai, Carbohydr. Polym., 2013, 92, 955–975.
61. H. Vaghari, H. Jafarizadeh-Malmiri, A. Berenjian and N. Anarjan, Sustainable Chem. Processes, 2013, 1, 1–12.
62. N. Yan and X. Chen, Nature, 2015, 524, 155–157.
63. D. Maiti, R. Das, T. Prabakar and S. Sen, Green Chem., 2022, 24, 3001–3008.
64. M. Akram, N. Arshad, M. K. Aktan and A. Braem, ACS Appl. Bio Mater., 2020, 3, 7052–7060.
65. E. Valiey and M. G. Dekamin, RSC Adv., 2022, 12, 437–450.
66. E. Valiey and M. G. Dekamin, Nanoscale Adv., 2022, 4, 294–308.
67. D. Astruc, F. Lu and J. R. Aranzaes, Angew. Chem., Int. Ed., 2005, 44, 7852–7872.
68. S. Karami, M. G. Dekamin, E. Valiey and P. Shakib, New J. Chem., 2020, 44, 13952–13961.
69. T. Chutimasakul, P. Na Nakhonpanom, W. Tirdtrakool, A. Intanin, T. Bunchuay, R. Chantiwas and J. Tantirungrotechai, RSC Adv., 2020, 10, 21009–21018.
70. M. Hasanpour Galehban, B. Zeynizadeh and H. Mousavi, RSC Adv., 2022, 12, 16454–16478.
71. L. Zhang, C. Yu, W. Zhao, Z. Hua, H. Chen, L. Li and J. Shi, J. Non-Cryst. Solids, 2007, 353, 4055–4061.
72. K. Li, J. Wang, Y. He, G. Cui, M. A. Abdulrazaq and Y. Yan, Chem. Eng. J., 2018, 351, 258–268.
73. H. Karimipour, A. Shahbazi and V. Vatanpour, J. Environ. Chem. Eng., 2021, 9, 104849.
74. D. W. Jenkins and S. M. Hudson, Chem. Rev., 2001, 101, 3245–3274.
75. X.-N. Zhao, G.-F. Hu, M. Tang, T.-T. Shi, X.-L. Guo, T.-T. Li and Z.-H. Zhang, RSC Adv., 2014, 4, 51089–51097.
76. M. Cupery, Ind. Eng. Chem., 1938, 30, 627–631.
77. S. A. El-Hakam, S. E. Samra, S. M. El-Dafrawy, A. A. Ibrahim, R. S. Salama and A. I. Ahmed, RSC Adv., 2018, 8, 20517–20533.
78. E. Valiey, M. G. Dekamin and Z. Alirezvani, Sci. Rep., 2021, 11, 11199.
79. P. R. Singh, D. U. Singh and S. D. Samant, Synlett, 2004, 2004, 1909–1912.
80. Y. T. Reddy, P. R. Reddy, M. N. Reddy, B. Rajitha and P. A. Crooks, Synth. Commun., 2008, 38, 3201–3207.
81. R. Nagarajan, C. J. Magesh and P. T. Perumal, Synthesis, 2004, 2004, 69–74.
82. T.-S. Jin, G. Sun, Y. W. Li and T.-S. Li, Green Chem., 2002, 4, 255–256.
83. B. Wang, J. He and R. C. Sun, Chin. Chem. Lett., 2010, 21, 794–797.
84. C. Huang, Y. Fu, H. Fu, Y. Jiang and Y. Zhao, Chem. Commun., 2008, 6333–6335.
85. K. Pedrood, M. Sherafati, M. Mohammadi-Khanaposhtani, M. S. Asgari, S. Hosseini, H. Rastegar, B. Larijani, M. Mahdavi, P. Taslimi and Y. Erden, Int. J. Biol. Macromol., 2021, 170, 1–12.
86. I. MaajidáTaily, Chem. Commun., 2021, 57, 631–634.
87. N. Nikooei, M. G. Dekamin and E. Valiey, Res. Chem. Intermed., 2020, 46, 3891–3909.
88. M. Rahman, I. Ling, N. Abdullah, R. Hashim and A. Hajra, RSC Adv., 2015, 5, 7755–7760.
89. L. Fišnerová, B. Brunová, Z. Kocfeldová, J. Tíkalová, E. Maturová and J. Grimová, Collect. Czech. Chem. Commun., 1991, 56, 2373–2381.
90. K. B. Gudasi, S. A. Patil, M. V. Kulkarni and M. Nethaji, Transition Met. Chem., 2009, 34, 325–330.
91. A. K. Tiwari, V. K. Singh, A. Bajpai, G. Shukla, S. Singh and A. K. Mishra, Eur. J. Med. Chem., 2007, 42, 1234–1238.
92. W. Armarego, Adv. Heterocycl. Chem., 1979, 24, 1–62.
93. S. H. Kim, S. H. Kim, T. H. Kim and J. N. Kim, Tetrahedron Lett., 2010, 51, 2774–2777.
94. P. H. Tran, T.-P. T. Bui, X.-Q. B. Lam and X.-T. T. Nguyen, RSC Adv., 2018, 8, 36392–36399.
95. A. Harutyunyan, Russ. J. Org. Chem., 2016, 52, 1012–1017.
96. A. Mishra and S. Batra, Synthesis, 2009, 2009, 3077–3088.
97. N. J. Vickers, Curr. Biol., 2017, 27, R713–R715.
98. T. H. Oude Munnink, E. G. de Vries, S. R. Vedelaar, H. Timmer-Bosscha, C. P. Schroder, A. H. Brouwers and M. N. Lub-de Hooge, Mol. Pharmaceutics, 2012, 9, 2995–3002.
99. A. A. Kalinin, A. D. Voloshina, N. V. Kulik, V. V. Zobov and V. A. Mamedov, Eur. J. Med. Chem., 2013, 66, 345–354.
100. H. Ghafuri, M. Ghafori Gorab and H. Dogari, Sci. Rep., 2022, 12, 4221.
101. M. Keshavarz, M. G. Dekamin, M. Mamaghani and M. Nikpassand, Sci. Rep., 2021, 11, 14457.
102. G. Yashwantrao, V. P. Jejurkar, R. Kshatriya and S. Saha, ACS Sustainable Chem. Eng., 2019, 7, 13551–13558.
103. N. Ghorashi, Z. Shokri, R. Moradi, A. Abdelrasoul and A. Rostami, RSC Adv., 2020, 10, 14254–14261.
104. M. Mohammadi and A. Ghorbani-Choghamarani, RSC Adv., 2022, 12, 2770–2787.
105. M. R. Anizadeh, M. A. Zolfigol, M. Yarie, M. Torabi and S. Azizian, Res. Chem. Intermed., 2020, 46, 3945–3960.
106. M. A. Diab, A. Z. El-Sonbati, D. M. D. Bader and M. S. Zoromba, J. Polym. Environ., 2012, 20, 29–36.
107. B. B. F. Mirjalili, Z. Zaghaghi and A. Monfared, J. Chin. Chem. Soc., 2020, 67, 197–201.
108. A. D. Rao, B. Vykunteswararao, T. Bhaskarkumar, N. R. Jogdand, D. Kalita, J. K. D. Lilakar, V. Siddaiah, P. D. Sanasi and A. Raghunadh, Tetrahedron Lett., 2015, 56, 4714–4717.
109. H. Ghafuri, N. Goodarzi, A. Rashidizadeh and M. A. Douzandegi Fard, Res. Chem. Intermed., 2019, 45, 5027–5043.
110. H. FaniMoghadam, M. G. Dekamin and N. Rostami, Res. Chem. Intermed., 2022, 48, 3061–3089.
111. H. R. Shaterian and F. Rigi, Res. Chem. Intermed., 2015, 41, 721–738.
112. R. Mekala, M. Madhubabu, G. Dhanunjaya, S. Regati, K. Chandrasekhar and J. Sarva, Synth. Commun., 2017, 47, 121–130.
113. S. U. Tekale, S. B. Munde, S. S. Kauthale and R. P. Pawar, Org. Prep. Proced. Int., 2018, 50, 314–322.
114. H. R. Shaterian, A. R. Oveisi and M. Honarmand, Synth. Commun., 2010, 40, 1231–1242.
115. J. Safaei-Ghomi, R. Teymuri and A. Bakhtiari, BMC Chem., 2019, 13, 26.

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Footnote

† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d2ra07319f

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