Published March 25, 2024
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Microwave-assisted organic synthesis of pyrroles (Review)
Authors/Creators
- 1. Medical University, Sofia, Bulgaria
- 2. Government College University Faisalabad, Faisalabad, Pakistan
Description
The detection of pyrrole rings in numerous organic compounds with various pharmacological activities, emphasizes its huge importance in medicinal chemistry. Thus, the synthesis of pyrroles continues to arouse interest and Paal-Knorr condensation is considered to be the main synthetic route. A significant advance has been made since the MW activation was introduced in the organic synthesis which can be confirmed with the rapid growth of the published papers on that topic. Microwave irradiation is gaining popularity since faster reaction time, higher yields, easier work-up and reduced energy input can be achieved. Furthermore, it appears in numerous green chemistry protocols. The aim of the current article was to provide insights into the microwave syntheses of pyrrole derivatives, focusing on the most used synthetic approaches - Paal-Knorr, Clauson-Kaas, Barton-Zard, Hantzsch and others. The article was divided into several sections starting with the principles of the microwave organic synthesis. Thereafter the structure and the main pharmacological effects of the pyrrole derivatives were examined. Subsequently, articles describing the synthesis of pyrroles via Paal-Knorr, Hantzsch, Clauson-Kaas and Barton– Zard were discussed. All the reviewed papers conclude a significant reduction of the reaction times after MW irradiation compared to conventional heating.
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References
- Abbat S, Dhaked D, Arfeenb M, Bharatam P (2015) Mechanism of the Paal–Knorr reaction: the importance of water mediated hemialcohol pathway. RSC Advances 5: 88353–88366. https://doi.org/10.1039/C5RA16246G
- Aghapoor K, Mohsenzadeh F, Darabi H, Rastgar S (2018) Microwave-induced calcium (II) chloride-catalyzed Paal–Knorr pyrrole synthesis: a safe, expeditious, and sustainable protocol. Research on Chemical Intermediates 44: 4063–4072. https://doi.org/10.1007/s11164-018-3355-7
- Aghapoor K, Mohsenzadeh F, Darabi H, Sayahi H (2021) Crystalline salicylic acid as an efficient catalyst for ultrafast Paal– Knorr pyrrole synthesis under microwave induction. Journal of Chemical Sciences 133: 38. https://doi.org/10.1007/s12039-021-01891-9
- Ahmad S, Alam O, Naim MJ, Shaquiquzzaman M, Alam MM, Iqbal M (2018) Pyrrole: An insight into recent pharmacological advances with structure activity relationship. European Journal of Medicinal Chemistry 157: 527–561. https://doi.org/10.1016/j.ejmech.2018.08.002.
- Amarnath V, Anthony D, Amarnath K, Valentine W, Wetterau L, Graham D (1991) Intermediates in the Paal-Knorr synthesis of pyrroles. The Journal of Organic Chemistry 56(24): 6924–6931. https://doi.org/10.1021/jo00024a040
- Andoh-Baidoo R, Danso R, Mukherjee S, Bandyopadhyay D, Banik B (2011) Microwave-induced n-bromosuccinimide-mediated novel synthesis of pyrroles via paal-knorr reaction. Heteroletters 1: 107–109.
- Algul O, Kaessler A, Apcin Y, Yilmaz A, Jose J (2008) Comparative studies on conventional and microwave synthesis of some benzimidazole, benzothiazole and indole derivatives and testing on inhibition of hyaluronidase. Molecules 13(4): 736–748. https://doi.org/10.3390/molecules13040736
- Asressu KH, Chan CK, Wang CC (2021) TMSOTf-catalyzed synthesis of trisubstituted imidazoles using hexamethyldisilazane as a nitrogen source under neat and microwave irradiation conditions. RSC Advances 11(45): 28061–28071. https://doi.org/10.1039/D1RA05802A
- Aydogan F, Demir A (2005) Clean and efficient microwave-solvent-free conversion of homochiral amines, α-amino alcohols and α-amino acids to their chiral 2-substituted pyrrole derivatives. Tetrahedron 61: 3019–3023. https://doi.org/10.1016/j.tet.2005.01.120
- Aydogan F, Yolacan C (2013) Clauson kaas pyrrole synthesis catalyzed by acidic ionic liquid under microwave irradiation. Journal of Chemistry 2013: 976724. https://doi.org/10.1155/2013/976724
- Bandgar B, Uppalla L, Kurule D (1999) Solvent-free one-pot rapid synthesis of 3-carboxycoumarins using focused microwaves. Green Chemistry Journal 1: 243–245. https://doi.org/10.1039/A905811G
- Bandyopadhyay D, Mukherjee S, Banik BK (2010) An expeditious synthesis of N-substituted pyrroles via microwave-induced iodine-catalyzed reactions under solventless conditions. Molecules 15(4): 2520–2525. https://doi.org/10.3390/molecules15042520
- Bhatewara A, Jetti SR, Kadre T, Paliwal P, Jain S (2013) Microwave-assisted synthesis and biological evaluation of dihydropyrimidinone derivatives as anti-inflammatory, antibacterial, and antifungal agents. International Journal of Medicinal Chemistry 2013: 197612. https://doi.org/10.1155/2013/197612
- Bharadwaj A, Scheidt K (2004) Catalytic multicomponent synthesis of highly substituted pyrroles utilizing a One-Pot Sila-Stetter/Paal−Knorr strategy. Organic Letters 6: 2465–2468. https://doi.org/10.1021/ol049044t
- Bianchi I, Forlani R, Minetto G, Paretto I, Regalia N, Taddei M, Raveglia L (2006) Solution phase synthesis of a library of tetrasubstituted pyrrole amides. Journal of Combinatorial Chemistry 8: 491–499. https://doi.org/10.1021/cc060008q
- Călinescu I, Vinatoru M, Ghimpețeanu D, Lavric V, Mason TJ (2021) A new reactor for process intensification involving the simultaneous application of adjustable ultrasound and microwave radiation. Ultrason Sonochem 77: 105701. https://doi.org/10.1016/j.ultsonch.2021.105701
- Cores A, Estévez V, Villacampaa M, Menéndez J (2016) Three-component access to 2-pyrrolin- 5-ones and their use in target-oriented and diversity-oriented synthesis. RSC Advances 6: 39433–39443. https://doi.org/10.1039/C6RA06317A
- Danks T (1999) Microwave assisted synthesis of pyrroles. Tetrahedron Letters 40: 3957–3960. https://doi.org/10.1016/S0040-4039(99)00620-6
- Donato L, Nasser II, Majdoub M, Drioli E (2022) Green chemistry and molecularly imprinted membranes. Membranes (Basel) 12(5): 472. https://doi.org/10.3390/membranes12050472
- Estévez V, Sridharan V, Sabaté S, Villacampa M, Menéndez C (2016) Three-component synthesis of pyrrole-related nitrogen heterocycles by a hantzsch-type process: Comparison between conventional and high-speed vibration milling conditions. Asian Jounral of Organic Chemistry 5: 652–662. https://doi.org/10.1002/ajoc.201600061
- Ferreira V, Souza M, Cunha A, Pereira L, Ferreira M (2001) Recent advances in the synthesis of pyrroles. Organic preparations and procedures international 33: 411–454. https://doi.org/10.1080/00304940109356613
- Frecentese F, Sodano F, Corvino A, Schiano ME, Magli E, Albrizio S, Sparaco R, Andreozzi G, Nieddu M, Rimoli MG (2023) The application of microwaves, ultrasounds, and their combination in the synthesis of nitrogen-containing bicyclic heterocycles. International Journal of Molecular Sciences 24(13): 10722. https://doi.org/10.3390/ijms241310722
- Gerling (1987) Microwave oven power: A technical review. Journal of Microwave Power and Electromagnetic Energy 22(4): 199–207. https://doi.org/10.1080/08327823.1987.11688024
- Gronnow M, White R, Clark J, Macquarrie D (2005) Energy efficiency in chemical reactions: a comparative study of different reaction techniques. Organic Process Research & Development 9(4): 516–518. https://doi.org/10.1021/op0498060
- Henary M, Kananda C, Rotolo L, Savino B, Owens EA, Cravotto G (2020) Benefits and applications of microwave-assisted synthesis of nitrogen containing heterocycles in medicinal chemistry. RSC Advances 10(24): 14170–14197. https://doi.org/10.1039/D0RA01378A
- Horikoshi S, Hamamura T, Kajitani M, Yoshizawa-Fujita M, Serpone N (2008) Green chemistry with a novel 5.8-GHz microwave apparatus. prompt One-Pot Solvent-Free synthesis of a major ionic liquid: The 1-Butyl-3-methylimidazolium tetrafluoroborate system. Organic Process Research & Development 12(6): 1089–1093. https://doi.org/10.1021/op800135t
- Ivan BC, Barbuceanu SF, Hotnog CM, Anghel AI, Ancuceanu RV, Mihaila MA, Brasoveanu LI, Shova S, Draghici C, Olaru OT, Nitulescu GM, Dinu M, Dumitrascu F (2022) New pyrrole derivatives as promising biological agents: Design, synthesis, characterization, in silico, and cytotoxicity evaluation. International Journal of Molecular Sciences 23(16): 8854. https://doi.org/10.3390/ijms23168854
- Jeelan Basha N, Basavarajaiah SM, Shyamsunder K (2022) Therapeutic potential of pyrrole and pyrrolidine analogs: an update. Molecular Diversity 26(5): 2915–2937. https://doi.org/10.1007/s11030-022-10387-8
- Jie X, Wang J, Gonzalez-Cortes S, Yao B, Li W, Gao Y, Dilworth JR, Xiao T, Edwards PP (2021) Catalytic activity of various carbons during the microwave-initiated deep dehydrogenation of hexadecane. JACS Au 1(11): 2021–2032. https://doi.org/10.1021/jacsau.1c00326
- Kochnev IA, Barkov AY, Zimnitskiy NS, Korotaev VY, Sosnovskikh VY (2022) Green and efficient construction of chromeno[3,4-c]pyrrole core via barton-zard reaction from 3-Nitro-2H-chromenes and ethyl isocyanoacetate. Molecules 27(23): 8456. https://doi.org/10.3390/molecules27238456
- Knorr (1885) Einwirkung des Diacetbernsteinsäureesters auf Ammoniak und primäre Aminbasen. Berichte der deutschen chemischen Gesellschaft 18: 299. https://doi.org/10.1002/cber.18850180154
- Kornienko A, La Clair JJ (2017) Covalent modification of biological targets with natural products through Paal-Knorr pyrrole formation. Natural Product Reports 34(9): 1051–1060. https://doi.org/10.1039/C7NP00024C
- Kizhakkekuttu R, Gopinadh M, Gopinathan A (2021) A solvent-free manganese(II) - catalyzed Clauson-Kaas protocol for the synthesis of N-aryl pyrroles under microwave irradiation. Journal of Heterocyclic Chemistry 59(1): 194–200. https://doi.org/10.1002/jhet.4372
- Leonardi M, Estévez V, Villacampa M, Menéndez J (2019) The Hantzsch pyrrole synthesis: Non- conventional variations and applications of a neglected classical reaction. Synthesis 51(04): 816–828. https://doi.org/10.1055/s-0037-1610320
- Lu W, Kuwabara J, Kanbara T (2013) Synthesis of π-conjugated polymer consisting of pyrrole and fluorene units by Ru-catalyzed site-selective direct arylation polycondensation. Macromolecular Rapid Communications 34(14): 1151–1156. https://doi.org/10.1002/marc.201300303
- Mallikarjuna Reddy G, Camilo Jr A, Raul Garcia J (2021) Pyrrole-2,5-dione analogs as a promising antioxidant agents: microwave-assisted synthesis, bio-evaluation, SAR analysis and DFT studies/interpretation. Bioorganic Chemistry 106: 104465. https://doi.org/10.1016/j.bioorg.2020.104465
- Mateev E, Georgieva M, Zlatkov A (2022) Pyrrole as an important scaffold of anticancer drugs: Recent advances. Journal of Pharmaceutical Sciences 25: 24–40. https://doi.org/10.18433/jpps32417
- Mathana B, Boyd R (2007) A density functional theory study of the mechanism of the Paal–Knorr pyrrole synthesis. Journal of Molecular Structure: Theochem 811: 97–107. https://doi.org/10.1016/j.theochem.2006.11.034
- Meera G, Rohit KR, Saranya S, Anilkumar G (2020) Microwave assisted synthesis of five membered nitrogen heterocycles. RSC Advances 10(59): 36031–36041. https://doi.org/10.1039/D0RA05150K
- Minetto G, Raveglia LF, Taddei M (2004) Microwave-assisted Paal-Knorr reaction. A rapid approach to substituted pyrroles and furans. Organic Letters 6(3): 389–392. https://doi.org/10.1021/ol0362820
- Minetto G, Raveglia L, Sega A, Taddei M (2005) Microwave-Assisted Paal–Knorr Reaction – Three-Step regiocontrolled synthesis of polysubstituted furans, pyrroles and thiophenes. EurJOC 24: 5277–5288. https://doi.org/10.1002/ejoc.200500387
- Mir RH, Mir PA, Mohi-Ud-Din R, Sabreen S, Maqbool M, Shah AJ, Shenmar K, Raza SN, Pottoo FH (2022) A comprehensive review on journey of pyrrole scaffold against multiple therapeutic targets. Anti-Cancer Agents in Medicinal Chemistry 22(19): 3291–3303. https://doi.org/10.2174/1871520622666220613140607
- Mohammadkhani L, Heravi MM (2020) Microwave-assisted synthesis of quinazolines and quinazolinones: An overview. Frontiers in Chemistry 8: 580086. https://doi.org/10.3389/fchem.2020.580086
- Mousavi S, Naeimi H, Ghasemi AH, Kermanizadeh S (2023) Nickel ferrite nanoparticles doped on hollow carbon microspheres as a novel reusable catalyst for synthesis of N-substituted pyrrole derivatives. Scientific Reports 13(1): 10840. https://doi.org/10.1038/s41598-023-37817-3
- Nandihalli N, Gregory DH, Mori T (2022) Energy-saving pathways for thermoelectric nanomaterial synthesis: Hydrothermal/Solvothermal, microwave-assisted, solution-based, and powder processing. Advanced Science (Weinh) 9(25): e2106052. https://doi.org/10.1002/advs.202106052
- Nguyen HT, Thuy Nguyen LH, Le Hoang Doan T, Tran PH (2019) A mild and efficient method for the synthesis of pyrroles using MIL-53(Al) as a catalyst under solvent-free sonication. RSC Advances 9(16): 9093–9098. https://doi.org/10.1039/C9RA01071H
- Ozaki T, Yorimitsu H, Perry G (2022) Late-stage sulfonic acid/sulfonate formation from sulfonamides via sulfonyl pyrroles. Tetrahedron 117–118: 132830. https://doi.org/10.1016/j.tet.2022.132830
- Paal (1884) Ueber die Derivate des Acetophenonacetessigesters und des Acetonylacetessigesters. Berichte der deutschen chemischen Gesellschaft 17: 2756. https://doi.org/10.1002/cber.188401702228
- Patil SA, Patil R, Miller DD (2011) Microwave-assisted synthesis of medicinally relevant indoles. Current Medicinal Chemistry 18(4): 615–637. https://doi.org/10.2174/092986711794480195
- Pawełczyk A, Sowa-Kasprzak K, Olender D, Zaprutko L (2018) Microwave (MW), Ultrasound (US) and Combined Synergic MW-US Strategies for rapid functionalization of pharmaceutical use phenols. Molecules 23(9): 2360. https://doi.org/10.3390/molecules23092360
- Philkhana SC, Badmus FO, Dos Reis IC, Kartika R (2021) Recent advancements in pyrrole synthesis. Synthesis (Stuttg) 53(9): 1531–1555. https://doi.org/10.1055/s-0040-1706713
- Polshettiwar V, Varma R (2010) Nano-organocatalyst: magnetically retrievable ferrite-anchored glutathione for microwave-assisted Paal–Knorr reaction, aza-Michael addition, and pyrazole synthesis. Tetrahedron 66: 1091–1097. https://doi.org/10.1016/j.tet.2009.11.015
- Rao S, Jothilingam S (2001) One-pot synthesis of pyrrole derivatives from (E)-1,4-diaryl-2- butene-1,4-diones. Tetrahedron Letters 42: 6595–6597. https://doi.org/10.1016/S0040-4039(01)01334-X
- Rodríguez AM, Prieto P, de la Hoz A, Díaz-Ortiz Á, Martín DR, García JI (2015) Influence of polarity and activation energy in microwave-assisted organic synthesis (MAOS). ChemistryOpen 4(3): 308–317. https://doi.org/10.1002/open.201402123
- Ruault P, Pilard J-F, Touaux B, Texier-Boullet F, Hamelin J (1994) Rapid generation of amines by microwave irradiation of ureas dispersed on clay. Synlett (11): 935–936. https://doi.org/10.1055/s-1994-23054
- Seipp K, Geske L, Opatz T (2021) Marine pyrrole alkaloids. Marine Drugs 19(9): 514. https://doi.org/10.3390/md19090514
- Singh DK, Kumar R (2023) Clauson-Kaas pyrrole synthesis using diverse catalysts: a transition from conventional to greener approach. Beilstein Journal of Organic Chemistry 19: 928–955. https://doi.org/10.3762/bjoc.19.71
- Sun J, Wang W, Yue Q (2016) Review on microwave-matter interaction fundamentals and efficient microwave-associated heating strategies. Materials (Basel) 9(4): 231. https://doi.org/10.3390/ma9040231
- Torres-Moya I, Harbuzaru A, Donoso B, Prieto P, Ponce Ortiz R, Díaz-Ortiz Á (2022) Microwave irradiation as a powerful tool for the preparation of n-type benzotriazole semiconductors with applications in organic field-effect transistors. Molecules 27(14): 4340. https://doi.org/10.3390/molecules27144340
- Trilleras J, Quiroga J, Hormaza A (2022) Synthesis of 3-Aroyl-4-heteroarylpyrrole derivatives by the Van Leusen method. Molbank 1: M1341. https://doi.org/10.3390/M1341
- Troisi L, Granito C, Pindinelli E (2010) Novel and recent synthesis and applications of β- lactams. Heterocyclic Scaffolds I 22: 101–209. https://doi.org/10.1007/7081_2009_12
- Venkatesan K, Ramakanth P, Anjaneyulu C (2020) Microwave assisted one pot synthesis of functionalized pyrrole derivatives catalyzed by uranyl nitrate hexa hydrate. CVR Journal of Science and Technology 18: 144–147. https://doi.org/10.32377/cvrjst1825
- Wan K, Chu T, Li B, Ming P, Zhang C (2023) Rational design of atomically dispersed metal site electrocatalysts for oxygen reduction reaction. Advanced Science (Weinh) 10(11): e2203391. https://doi.org/10.1002/advs.202203391
- Wang HY, Mueller DS, Sachwani RM, Kapadia R, Londino HN, Anderson LL (2011) Regioselective synthesis of 2,3,4- or 2,3,5-trisubstituted pyrroles via [3,3] or [1,3] rearrangements of O-vinyl oximes. The Journal of Organic Chemistry 76(9): 3203–3221. https://doi.org/10.1021/jo200061b
- Werner S, Iyer PS, Fodor MD, Coleman CM, Twining LA, Mitasev B, Brummond KM (2006) Solution-phase synthesis of a tricyclic pyrrole-2-carboxamide discovery library applying a stetter- Paal-Knorr reaction sequence. Journal of Combinatorial Chemistry 8(3): 368–380. https://doi.org/10.1021/cc050160c
- Wilson M, Filzen G, Welmaker G (2009) A microwave-assisted, green procedure for the synthesis of N-aryl sulfonyl and N-aryl pyrroles. Tetrahedron Letters 50: 4807–4809. https://doi.org/10.1016/j.tetlet.2009.06.079
- Yang R, Chen J (2021) Mechanistic and machine learning modeling of microwave heating process in domestic ovens: A review. Foods 10(9): 2029. https://doi.org/10.3390/foods10092029
- Zhang L, Zhang J, Ma J, Cheng DJ, Tan B (2017) Highly atroposelective synthesis of arylpyrroles by catalytic asymmetric paal-knorr reaction. Journal of the American Chemical Society 139(5): 1714–1717. https://doi.org/10.1021/jacs.6b09634