Abstract
A library of new spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-2′,10,12-trione derivatives has been prepared in an efficient, one-pot pseudo four-component method mediated by a reusable heterogeneous nano-ordered mesoporous SO3H functionalized-silica (MCM-41-SO3H) catalyst. Excellent yields, short reaction times, as well as convenient non-chromatographic purification of the products and environmental benefits such as green and metal-free conditions constitute the main advantages of the developed synthetic methodology. The obtained fused indole-indenone dyes would be of interest to pharmaceutical and medicinal chemistry. Furthermore, due to their sensitivity to pH changes, they could be used as novel pH indicators.
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Introduction
Multicomponent reactions are extensively used as an efficient tool to construct complex molecular motifs of important pharmaceutics, plant protection compounds, functional materials, and building blocks of a variety of fine chemicals. Such methodology usually satisfies rigid requirements of green chemistry and is characterized by atom-economy, synthetic convergency, simple purification protocols, and decreased usage of expensive solvents and reagents1,2,3,4,5,6,7,8,9,10,11,12. In recent years, the multicomponent reaction strategy has been applied for the synthesis of spirooxindoles and other privileged isatine derivatives13,14,15,16,17,18,19,20.
Many pharmaceutically important compounds possess a structural motif of merged indole and indenone cores21,22,23,24,25,26. The indenopyridine motif is found in many alkaloids and medicines, which exhibit anti-breast cancer27, cytotoxic28,29,30, calcium modulatory31, and other types of biological activities. At the same time, some such heterocycles are pH-indicators32, while others are used as building blocks in the synthesis of DNA inter-chelating drugs33 (Fig. 1).
Examples of bioactive indenopyridines.
A literature survey indicates a significantly small number of known methods for the synthesis of spiroindole core-based compounds. Several approaches to the synthesis of indenone-fused heterocycles from isatins, aromatic amines and 1,3-indanedione have been performed under various conditions, e.g. catalysis by p-toluenesulfonic acid34,35, sulfonated polyethylene glycol (PEG-OSO3H), N-methyl-2-pyrrolidonium dihydrogen phosphate ionic liquid36, oxalic acid dehydrate, a proline-based low transition temperature mixture37, and a zinc terephthalate metal–organic framework38. Despite some advantages, most of these methods have significant drawbacks, including the application of toxic, expensive solvents and catalysts, as well as complicated purification procedures and waste management protocols. Instead, heterogeneous recoverable catalysts used in the chemical industry and research labs make these processes much more environmentally friendly39,40,41,42,43.
In this study, we have focused on a heterogeneous acidic catalyst, which is easily prepared and has excellent activity and chemical stability. It can also be separated from the product after the reaction and be reused. Such parameters provide additional cost efficiency and environmental safety to the developing procedures44,45,46.
MCM-41 is a solid mesoporous nano-ordered silica with a large surface area and a regular structure. The diameter of the MCM-41 pores is distributed between 1.5 and 10 nm. It bears merely weak hydrogen bonding Si–OH sites and therefore at most only slightly acidic47,48. Its acidity could be improved, however, by substituting the Si atoms on its surface with Al49, B50, and Zn51, and or by functionalizing the MCM-41 surface with an alkyl sulfonic acid anchoring group52,53, succinamic acid54, or –SO3H55,56,57. Due to a large number of silanol groups, anchoring of inorganic –SO3H to the MCM-41 surface is very practical58. Such a readily accessible compound (MCM-41-SO3H) is non-toxic, recyclable, and reusable. Hence, MCM-41-SO3H is extensively applied in many chemical processes.
As an extension of our continuous studies on the application of heterogeneous catalytic systems to the synthesis of different classes of pharmaceutically important compounds and to the development of green multicomponent reactions (MCRs)57,59,60,61,62,63,64, herein we report a straightforward approach leading to an effective, one-pot pseudo four-components synthesis of spiro[diindenopyridine-indoline]triones. The reaction between 1,3-indandione (1), aromatic amines (2a-g), and isatins (3a-h) in DMF is catalyzed by MCM-41-SO3H affording spiro[diindenopyridine-indoline]triones with good to excellent yields (Scheme 1).
Synthesis of spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-2′,10,12-triones.
Results and discussion
Characterization of the MCM-41-SO3H
The MCM-41-SO3H was prepared according to our previous reports57,59,60 and characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and Brunauer–Emmett–Teller analysis (BET). The FTIR spectrum of the catalyst has been shown in Fig. 2. The bands at 1325 and 1288 cm−1 correspond to the asymmetric and symmetric stretching vibrations of the SO3H group. A wide band in the area of 3400–3200 cm−1 is related to the O–H stretching vibration of the hydroxyl groups. Moreover, stretching vibrations of Si–O–Si are indicated by sharp bands at 1170 and 850 cm−165,66.
FT-IR spectra of nano-ordered MCM-41 (a), and MCM-41-SO3H (b).
The SEM images of the fresh and recovered MCM-41-SO3H have been shown in Fig. 3 and confirm the nanoscale size of the synthesized particles. The size of most particles was in the range of 50–90 nm. As can be seen, the particles are aggregated, due to the strong hydrogen bonding between the acidic moieties. The EDX analysis of the fresh catalyst proved the presence of O, Si, and S atoms in the MCM-41-SO3H structure with a uniform distribution of the sulfonic acid groups (Fig. 4).
The SEM images of the MCM-41-SO3H: the fresh catalyst (left), and the recovered one (right).
The EDX analysis of the fresh MCM-41-SO3H.
According to the obtained results from the N2 adsorption–desorption diagram (Fig. 5), the BET and the Langmuir surface area of the MCM-41-SO3H were 223 and 303 m2 g−1, respectively. The BET adsorption average pore width (4 V/A) was measured to be 7.2 nm. The catalyst surface area and porosity properties are in good agreement with a typical mesoporous material.
The N2 adsorption–desorption isotherms of the MCM-41-SO3H.
Synthesis of spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-2′,10,12-triones: an optimization of the reaction conditions
As it was mentioned above, our study aimed to discover an environmentally benign protocol for the synthesis of diversified spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-2′,10,12-triones, which would satisfy the requirements of green chemistry67,68. Desired products were obtained in one-pot multicomponent reactions between 1,3-indanedione (1), anilines (2), and isatins (3). To find optimal conditions, several variables affecting the reaction yield were assessed.
Assessment of the effect of the catalyst used
The catalytic efficiency of various members of the MCM-41 family (Al-MCM-41, Fe-MCM-41, MCM-41-NH2, and MCM-41-SO3H), as well as several other solid acid catalysts such as cellulose-SO3H, pectin, carboxymethyl cellulose, and hydroxyapatite were compared. The results presented in Table 1 indicate that a higher yield of the benchmark reaction between 1, 2a, and 3a, which furnished 5-(phenyl)-5H-spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-2′,10,12-trione (4a) was observed, when MCM-41-SO3H was used. The effectiveness of this catalyst could be rationalized taking the high Brönsted acidity of the catalyst used and its appropriate pore size into consideration. The loading of MCM-41-SO3H was also optimized. The yields of 64% and 89% 4a were obtained when 5 and 10 mg of MCM-41-SO3H catalyst were used in a 1 mmol scale of the reaction at 100 °C for 2 h (Table 1, entries 11 and 12); whereas a 94% yield was achieved after the first 20 min of the reaction in the presence of 20 mg of the catalyst (Table 1, entry 6).
Assessment of the effect of the solvent and temperature
The effect of various polar and non-polar, protic and aprotic solvents (EtOAc, n-hexane, EtOH, CH3CN, DMF, and DMSO) on the yield of the model reaction was also evaluated (Table 2, entries 1 and 4–8).
The polar aprotic solvent DMF was found to be a solvent of choice in this reaction (Table 2, entry 1). The solvent-free reaction ran in identical conditions -but without any solvent- with a poor yield, event after a long reaction time (Table 2, entry 9). On the other hand, the evaluation of the temperature influence on the yield of 4a indicated that higher temperature resulted in an improved yield in a shorter reaction time (Table 2, entries 1–3).
In comparison with other catalysts used in the similar reaction reported previously (Table 3), the heterogeneous MCM-41-SO3H was beneficial, offering higher sustainability and better efficiency in the synthesis of 4a. In addition, the atom economy of the protocol proposed herein and the waste exclusion proved its greenness as well.
Assessment of the substrate scope
In general, high to excellent yields of spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-2′,10,12-triones 4a-y with a broad range of substituents were achieved in a short reaction time (Table 4).
In comparison with the EWG-substituted substrates (Table 4, entries 3, 15–18), higher yields and shorter reaction times were observed for EDG-substituted isatins and aromatic amines (Table 4, entries 2, 5, 8, 12, 16).
The study on catalyst stability and reusability
The possibility of recovering and reusing the catalyst was assessed in four consecutive runs for the benchmark reaction leading to 4a. After each run, the catalyst was filtered off and washed with n-hexane and acetone. Next, it was dried at 60 °C for 0.5 h. The recycled catalyst was then subjected to the next run of the model reaction. A significant maintaining of the catalytic activity of MCM-41-SO3H in each run of the reaction was observed (Fig. 6).
Reusability of the MCM-41-SO3H catalyst in four consecutive runs.
The FT-IR spectra of the fresh and the recovered MCM-41-SO3H catalyst after the fourth run indicated that its structure remained unchanged (Fig. 7).
The FT-IR spectra of the fresh MCM-41-SO3H (a), and the recovered one (b).
Possible mechanism
A plausible mechanism of the reaction leading to spiro[diindenopyridine-indoline]triones is outlined in Scheme 2.
Proposed catalytic role of the MCM-41-SO3H in the multicomponent condensation leading to the spirodiindenopyridine indoline 4a.
According to the proposed mechanism, acidic SO3H groups located on the surface of MCM-41-SO3H activate the carbonyl group of isatin (3a) to facilitate initial nucleophilic addition of the enolic form of 1,3-indanedione (1) affording the intermediate I. The addition of 2a to the intermediate I, followed by a cyclization reaction, furnishes the product 4a.
Study of the spectral properties of the obtained products 4a–4y.
The UV–Vis spectra of 4a–4y were obtained in methanol and reported in Table 5. They showed a maximum absorption wavelength (λmax) in the range of 422–435 nm and a molar extinction coefficient (ɛ) of (1.08–2.99) × 105 L mol−1 cm−1.
The Spiro[diindenopyridine indoline]triones with a hydrogen atom at indoline nitrogen may undergo reversible deprotonation and can be used as pH chemo-sensors. The product 4a was examined as a pH indicator and showed a visible color change at pH ca. 11, from red (in the acidic media) to deep blue (in the basic conditions) (Fig. 8). However, the solution of N-substituted isatins (e.g. 4w) showed no remarkable color change in an alkali solution.
Spectral changes of the 5-(phenyl)-5H-spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-2′,10,12-trione (4a) (Metanol, 100 ppm) at different pH values.
The UV–Vis absorption of the compound 4a was measured in the pH range from 3 to 12.5. As shown in Fig. 8, beginning from ca. pH 9, a second absorption peak around 530 nm appears. The spectral data is given in Table 6. Whereas the N–H isatins solution displayed similar behavior, N-substituted isatins showed no color change in a wide range of pH. It seems that the color change in dye 4a is due to the deprotonation of the NH group in the indoline unit (Scheme 3).
The pH effect on the Π-system of spirodiindenopyridine indolines derivatives.
Conclusions
To summarize, we have herein reported a straightforward atom-economical method of synthesis of spiro[diindenopyridine indoline]triones mediated by a safe heterogeneous recyclable catalyst MCM-41-SO3H, which could be used for at least 4 runs without any significant loss of its activity. Among other advantages of the current protocol, we could emphasize excellent yields, short reaction times, high atom economy as well as simple isolation and purification procedures for both the catalyst and products. The presented approach leading to spiro[diindenopyridine-indoline]triones can be of interest to medicinal and pharmaceutical chemistry. Furthermore, some products exhibit a pH indicator activity proven by a visible color change in the basic pH ranges (Supplementary Information S1).
References
Zhu, J. & Bienaymé, H. Multicomponent reactions. (John Wiley & Sons, 2006).
Arcadia, C. E. et al. Multicomponent molecular memory. Nat. Commun. 11, 1–8 (2020).
Dömling, A., Wang, W. & Wang, K. Chemistry and biology of multicomponent reactions. Chem. Rev. 112, 3083–3135. https://doi.org/10.1021/cr100233r (2012).
Ganem, B. Strategies for innovation in multicomponent reaction design. Acc. Chem. Res. 42, 463–472 (2009).
Boukis, A. C., Reiter, K., Frölich, M., Hofheinz, D. & Meier, M. A. Multicomponent reactions provide key molecules for secret communication. Nat. Commun. 9, 1–10 (2018).
Cioc, R. C., Ruijter, E. & Orru, R. V. Multicomponent reactions: Advanced tools for sustainable organic synthesis. Green Chem. 16, 2958–2975 (2014).
Bienaymé, H., Hulme, C., Oddon, G. & Schmitt, P. Maximizing synthetic efficiency: Multi‐component transformations lead the way. Chem. Eur. J. 6, 3321–3329 (2000).
Müller, T. J. Multicomponent reactions in the synthesis of heterocycles. Chem. Heterocycl. Compd 53, 381 (2017).
Ghashghaei, O. et al. Multiple multicomponent reactions: unexplored substrates, selective processes, and versatile chemotypes in biomedicine. Chem. Eur. J. 24, 14513–14521 (2018).
Kakuchi, R. The dawn of polymer chemistry based on multicomponent reactions. Polym. J. 51, 945–953. https://doi.org/10.1038/s41428-019-0209-0 (2019).
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. Sci. Rep. 10, 10646. https://doi.org/10.1038/s41598-020-67592-4 (2020).
Eckert, H. Diversity oriented syntheses of conventional heterocycles by smart multi component reactions (MCRs) of the last decade. 17, 1074–1102 (2012).
Zarei, M., Sepehrmansourie, H., Zolfigol, M. A., Karamian, R. & Farida, S. H. M. Novel nano-size and crab-like biological-based glycoluril with sulfonic acid tags as a reusable catalyst: Its application to the synthesis of new mono-and bis-spiropyrans and their in vitro biological studies. New J. Chem. 42, 14308–14317 (2018).
Moosavi-Zare, A. R., Zolfigol, M. A., Noroozizadeh, E., Salehi-Moratab, R. & Zarei, M. Silica-bonded 1, 4-diaza-bicyclo [2.2. 2] octane-sulfonic acid chloride catalyzed synthesis of spiropyran derivatives. J. Mol. Catal. A Chem. 420, 246–253 (2016).
Esmaeilpour, M., Javidi, J. & Divar, M. A green one-pot three-component synthesis of spirooxindoles under conventional heating conditions or microwave irradiation by using Fe3O4@ SiO2-imid-PMAn magnetic porous nanospheres as a recyclable catalyst. J. Magn. Magn. Mater. 423, 232–240 (2017).
Jadidi, K., Ghahremanzadeh, R. & Bazgir, A. Spirooxindoles: Reaction of 2, 6-diaminopyrimidin-4 (3H)-one and isatins. Tetrahedron 65, 2005–2009 (2009).
Singh, R. & Vince, R. 2-Azabicyclo [2.2. 1] hept-5-en-3-one: chemical profile of a versatile synthetic building block and its impact on the development of therapeutics. Chem. Rev. 112, 4642–4686 (2012).
Borad, M. A., Bhoi, M. N., Prajapati, N. P. & Patel, H. D. Review of synthesis of spiro heterocyclic compounds from isatin. Synth. Commun. 44, 897–922 (2014).
Liu, Y., Wang, H. & Wan, J. Recent advances in diversity oriented synthesis through isatin-based multicomponent reactions. Asian J. Organ. Chem. 2, 374–386 (2013).
Sun, J., Shen, G.-L., Huang, Y. & Yan, C.-G. Formation of diverse polycyclic spirooxindoles via three-component reaction of isoquinolinium salts, isatins and malononitrile. Sci. Rep. 7, 41024. https://doi.org/10.1038/srep41024 (2017).
Casapullo, A., Bifulco, G., Bruno, I. & Riccio, R. New bisindole alkaloids of the topsentin and hamacanthin classes from the Mediterranean marine sponge Rhaphisia lacazei. J. Nat. Prod. 63, 447–451 (2000).
Ziarani, G. M., Moradi, R., Ahmadi, T. & Lashgari, N. Recent advances in the application of indoles in multicomponent reactions. RSC Adv. 8, 12069–12103 (2018).
Xu, M. et al. Cobalt-catalyzed regioselective syntheses of indeno [2, 1-c] pyridines from nitriles and diynes bearing propargyl fragments. Org. Biomol. Chem. 16, 8761–8768 (2018).
Sundberg, R. Indoles Academic Press. San Diego, 113 (1996).
Gribble, G. W. Heterocyclic Scaffolds II:: Reactions and Applications of Indoles. Vol. 26 (Springer Science & Business Media, 2010).
Patravale, A. A. et al. Contemporary development in sequential Knoevenagel, Michael addition multicomponent reaction for the synthesis of 4-Aryl-5-oxo-5H-indeno[1,2-b]pyridine-3-carbonitrile. Res. Chem. Intermed. 42, 2919–2935. https://doi.org/10.1007/s11164-015-2187-y (2016).
Hati, S. et al. Spiro[pyrrolidine-3, 3´-oxindole] as potent anti-breast cancer compounds: Their design, synthesis, biological evaluation and cellular target identification. Sci. Rep. 6, 32213. https://doi.org/10.1038/srep32213 (2016).
Miri, R., Javidnia, K., Hemmateenejad, B., Azarpira, A. & Amirghofran, Z. Synthesis, cytotoxicity, QSAR, and intercalation study of new diindenopyridine derivatives. Bioorg. Med. Chem. 12, 2529–2536 (2004).
Tugrak, M., Gul, H. I., Sakagami, H., Gulcin, I. & Supuran, C. T. New azafluorenones with cytotoxic and carbonic anhydrase inhibitory properties: 2-Aryl-4-(4-hydroxyphenyl)-5H-indeno [1, 2-b] pyridin-5-ones. Bioorg. Chem. 81, 433–439 (2018).
Vaca, J., Salazar, F., Ortiz, A. & Sansinenea, E. Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study. J. Antibiot. 1–5 (2020).
Safak, C., Simsek, R., Altas, Y., Boydag, S. & Erol, K. 2-methyl-3-acetyl-4-aryl-5-oxo-1, 4-dihydro-5H indeno (1, 2-b) pyridine derivatives studies and their calcium antagonistic activities. Boll. Chim. Farm. 136, 665–669 (1997).
Shirini, F., Beigbaghlou, S. S., Atghia, S. V. & Mousazadeh, S.A.-R. Multi-component one-pot synthesis of unsymmetrical dihydro-5H-indeno [1, 2-b] quinolines as new pH indicators. Dyes Pigm. 97, 19–25 (2013).
Sunami, T. et al. Combination effects of TAS-103, a novel dual topoisomerase I and II inhibitor, with other anticancer agents on human small cell lung cancer cells. Cancer Chemother. Pharmacol. 43, 394–401 (1999).
Ghahremanzadeh, R., Ahadi, S., Shakibaei, G. I. & Bazgir, A. Grindstone chemistry: one-pot synthesis of spiro [diindenopyridine-indoline] triones and spiro [acenaphthylene-diindenopyridine] triones. Tetrahedron Lett. 51, 499–502 (2010).
Ghahremanzadeh, R., Imani Shakibaei, G., Ahadi, S. & Bazgir, A. One-pot, pseudo four-component synthesis of a spiro [diindeno [1, 2-b: 2′, 1′-e] pyridine-11, 3′-indoline]-trione Library. J. Combin. Chem. 12, 191–194 (2010).
Sindhu, J., Singh, H. & Khurana, J. Efficient synthesis of spiro [diindenopyridine-indoline] triones catalyzed by PEG-OSO3H-H2O and [NMP] H2PO4. Synth. Commun. 45, 202–210 (2015).
Chandam, D. R. et al. Oxalic acid dihydrate and proline based low transition temperature mixture: An efficient synthesis of spiro [diindenopyridine-indoline] triones derivatives. J. Mol. Liq. 219, 573–578 (2016).
Ghasemzadeh, M. A., Abdollahi-Basir, M. H. & Mirhosseini-Eshkevari, B. Multi-component synthesis of spiro [diindeno [1, 2-b: 2′, 1′-e] pyridine-11, 3′-indoline]-triones using zinc terephthalate metal-organic frameworks. Green Chem. Lett. Rev. 11, 47–53 (2018).
Moosavi-Zare, A. R. et al. Synthesis and characterization of acetic acid functionalized poly (4-vinylpyridinium) salt as new catalyst for the synthesis of spiropyran derivatives and their biological activity. J. Mol. Catal. A: Chem. 425, 217–228 (2016).
Sepehrmansourie, H., Zarei, M., Taghavi, R. & Zolfigol, M. A. Mesoporous ionically tagged cross-linked poly (vinyl imidazole) s as novel and reusable catalysts for the preparation of N-heterocycle spiropyrans. ACS Omega 4, 17379–17392 (2019).
Wilson, K. & Lee, A. F. Heterogeneous catalysts for clean technology: spectroscopy, design, and monitoring. (John Wiley & Sons, 2013).
Li, Z. et al. Well-defined materials for heterogeneous catalysis: From nanoparticles to isolated single-atom sites. Chem. Rev. 120, 623–682 (2019).
Yaghoubi, A., Dekamin, M. G. & Karimi, B. Propylsulfonic acid-anchored isocyanurate-based periodic mesoporous organosilica (PMO-ICS-PrSO 3 H): A highly efficient and recoverable nanoporous catalyst for the one-pot synthesis of substituted polyhydroquinolines. Catal. Lett. 147, 2656–2663 (2017).
Clark, J. H. Green chemistry: Today (and tomorrow). Green Chem. 8, 17–21 (2006).
Kefayati, H., Bazargard, S. J., Vejdansefat, P., Shariati, S. & Kohankar, A. M. Fe3O4@ MCM-41-SO3H@[HMIm][HSO4]: An effective magnetically separable nanocatalyst for the synthesis of novel spiro [benzoxanthene-indoline] diones. Dyes Pigm. 125, 309–315 (2016).
Shaabani, S., Naimi-Jamal, M. R. & Maleki, A. Synthesis of 2-hydroxy-1, 4-naphthoquinone derivatives via a three-component reaction catalyzed by nanoporous MCM-41. Dyes Pigm. 122, 46–49 (2015).
Zhang, W., Pauly, T. R. & Pinnavaia, T. J. Tailoring the framework and textural mesopores of HMS molecular sieves through an electrically neutral (S° I°) assembly pathway. Chem. Mater. 9, 2491–2498 (1997).
Ng, E.-P. & Mintova, S. Nanoporous materials with enhanced hydrophilicity and high water sorption capacity. Microporous Mesoporous Mater. 114, 1–26 (2008).
Iwanami, K., Seo, H., Choi, J.-C., Sakakura, T. & Yasuda, H. Al-MCM-41 catalyzed three-component Strecker-type synthesis of α-aminonitriles. Tetrahedron 66, 1898–1901 (2010).
Dekamin, M., Mokhtari, Z. & Karimi, Z. Nano-ordered B-MCM-41: An efficient and recoverable solid acid catalyst for three-component Strecker reaction of carbonyl compounds, amines and TMSCN. Sci. Iran. 18, 1356–1364 (2011).
Kiomarsipour, N., Razavi, R. S. & Ghani, K. Improvement of spacecraft white thermal control coatings using the new synthesized Zn-MCM-41 pigment. Dyes Pigm. 96, 403–406 (2013).
Karimi, B. & Zareyee, D. A high loading sulfonic acid-functionalized ordered nanoporous silica as an efficient and recyclable catalyst for chemoselective deprotection of tert-butyldimethylsilyl ethers. Tetrahedron Lett. 46, 4661–4665 (2005).
Das, D., Lee, J.-F. & Cheng, S. Selective synthesis of Bisphenol-A over mesoporous MCM silica catalysts functionalized with sulfonic acid groups. J. Catal. 223, 152–160 (2004).
Mathew, A. et al. Rhodamine 6G assisted adsorption of metanil yellow over succinamic acid functionalized MCM-41. Dyes Pigm. 131, 177–185 (2016).
Fathollahi, M., Rostamizadeh, S. & Amani, A. M. A clean, mild, and efficient preparation of aryl 14H-benzo [a, j] xanthene leuco-dye derivatives via nanocatalytic MCM-41-SO3H under ultrasonic irradiation in aqueous media. Comb. Chem. High Throughput Screen 21, 5–13 (2018).
Safaei, S. et al. SO 3 H-functionalized MCM-41 as an efficient catalyst for the combinatorial synthesis of 1H-pyrazolo-[3, 4-b] pyridines and spiro-pyrazolo-[3, 4-b] pyridines. J. Iran. Chem. Soc. 14, 1583–1589 (2017).
Dekamin, M. G. & Mokhtari, Z. Highly efficient and convenient Strecker reaction of carbonyl compounds and amines with TMSCN catalyzed by MCM-41 anchored sulfonic acid as a recoverable catalyst. Tetrahedron 68, 922–930 (2012).
Wilson, K. & Clark, J. H. Solid acids and their use as environmentally friendly catalysts in organic synthesis. Pure Appl. Chem. 72, 1313–1319 (2000).
Ali, E., Naimi-Jamal, M. & Dekamin, M. Highly efficient and rapid synthesis of imines in the presence of nano-ordered MCM-41-SO3H heterogeneous catalyst. Sci. Iran. 20, 592–597 (2013).
Tourani, H., Naimi-Jamal, M. R., Dekamin, M. G. & Amirnejad, M. A rapid, convenient and chemoselective synthesis of acylals from aldehydes catalyzed by reusable nano-ordered MCM-41-SO3H. C. R. Chim. 15, 1072–1076 (2012).
Lima, C. G., Moreira, N. M., Paixao, M. W. & Corrêa, A. G. Heterogenous green catalysis: Application of zeolites on multicomponent reactions. Curr. Opin. Green Sustain. Chem. 15, 7–12 (2019).
Villabrille, P. I., Palermo, V., Sathicq, A. G., Vazquez, P. G. & Romanelli, G. P. Transition metal-doped heteropolyacid catalysts for the suitable multicomponent synthesis of monastrol and bioactive related compounds. Curr. Org. Chem. 22, 94–100 (2018).
Alvim, H. G., da Silva Junior, E. N. & Neto, B. A. What do we know about multicomponent reactions? Mechanisms and trends for the Biginelli, Hantzsch, Mannich, Passerini and Ugi MCRs. Rsc Adv. 4, 54282–54299 (2014).
Taylor, D. Heterogeneous catalysis. Nature 222, 51–51 (1969).
Zolfigol, M. A. Silica sulfuric acid/NaNO2 as a novel heterogeneous system for production of thionitrites and disulfides under mild conditions. Tetrahedron 57, 9509–9511. https://doi.org/10.1016/S0040-4020(01)00960-7 (2001).
Zolfigol, M. A., Salehi, P., Shiri, M., Faal Rastegar, T. & Ghaderi, A. Silica sulfuric acid as an efficient catalyst for the Friedländer quinoline synthesis from simple ketones and ortho-aminoaryl ketones under microwave irradiation. J. Iran. Chem. Soc. 5, 490–497. https://doi.org/10.1007/BF03246007 (2008).
Anastas, P. T. & Tundo, P. Green chemistry: Challenging perspectives (Oxford University Press, Oxford, 2000).
Perosa, A. & Zecchini, F. Methods and reagents for green chemistry: an introduction. (John Wiley & Sons, 2007).
Acknowledgements
We are grateful for the financial support from The Research Council of Iran University of Science and Technology (IUST), Tehran, Iran. We would also like to acknowledge the support of The Iran Nanotechnology Initiative Council (INIC), Iran.
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(1) M.F. worked on the topic as her MSc. Thesis and prepared the initial draft of the manuscript. (2) M.R.N.-J. is the first supervisor of Miss Fathi and Dr. Leila Panahi as his MSc. and postdoc researcher, respectively. Also, he edited the manuscript completely. (3) M.G.D. is the advisor of Miss Fathi. Also, he edited, revised and submitted the manuscript completely. (4) L.P. worked closely with Miss Fathi for doing experimental section and interpreting of the characterization data. (5) O.M.D. prepared HRMS, H and C NMR spectral data as well as their assignments especially for novel compounds. He also edited initial draft of the manuscript.
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Fathi, M., Naimi-Jamal, M.R., Dekamin, M.G. et al. 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. Sci Rep 11, 4820 (2021). https://doi.org/10.1038/s41598-021-84209-6
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DOI: https://doi.org/10.1038/s41598-021-84209-6
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