Abstract
A series of diverse polyfunctionalized triheterocyclic benzothiazoles were easily prepared in excellent yields via the Biginelli reaction of 2-aminobenzothiazole with substituted benzaldehydes and \(\upalpha \)-methylene ketones using \(\hbox {FeF}_{3}\) as an expeditious catalyst under solvent-free conditions. The protocol provides a practical and straightforward approach toward highly functionalized triheterocyclic benzothiazole derivatives in excellent yields. The reaction was conveniently promoted by \(\hbox {FeF}_{3}\) and the catalyst could be recovered easily after the reaction and reused without any loss of its catalytic activity. The advantageous features of this methodology are high atom economy, operational simplicity, shorter reaction time, convergence, and facile automation.
References
Singh SP, Mishra RS, Parmar SS, Brumieve SJ (1975) Synthesis of 2-(4 arylthiosemicarbazidocarbonylthio) benzthiazoles and their monamine oxidase inhibitory and anticonvulsant properties. J Pharm Sci 64:1245–1247. doi:10.1002/jps.2600640730
Hutchinson I, Chua MS, Browne HL, Trapani V, Bradshaw TD, Westwell AD, Stevens MFG (2001) Antitumor benzothiazoles. 14. Synthesis and in vitro biological properties of fluorinated 2-(4-aminophenyl) benzothiazoles. J Med Chem 44:1446–1455. doi:10.1021/jm001104n
Singh SP, Vaid PK (1986) Some new 2-(4-butyl-3,5-dimethylpyrazol-1-yl)-6-substituted benzothiazoles, were assessed for their anti-inflammatory activity. Indian J Chem 25B:288–291
Pande AV, Lokhande SR, Patel MR, Khadse BG (1982) Synthesis and study of 2-substituted alkyl or aryl, amino 6-methyl benzothiazoles as antituberculosis agents. Indian Drugs 19:342–345
Klusa V (1995) Cerebrocrast, neuroprotectant, cognition enhancer. Drugs Future 20:135–139
Boer R, Gekeler V (1995) Chemosensitizers in tumor therapy: New compounds promise better efficacy. Drugs Future 20:499
Bretzel RG, Bollen CC, Maeser E, Federlin KF (1993) Nephroprotective effects of nitrendipine in hypertensive type I and type II diabetic patients. Am J Kidney Dis 21:S53–S64
Choudhary S, Kini SG, Mubeen M (2013) Antioxidant activity of novel coumarin substituted benzothiazole derivatives. Der Pharma Chemica 5:213–222
Hopper RJ (1993) 2-(Isopropylsulfinyl)-benzothiazole as a delayed action thiazole accelerator. Rubber Chem Technol 66:623–633. doi:10.5254/1.3538334
Zhang XH, Wong OY, Gao ZQ, Lee CS, Kwong HL, Wu SK (2001) A new blue-emitting benzothiazole derivative for organic electroluminescent devices. Mater Sci Eng B 85:182–185. doi:10.1016/S0921-5107(01)00607-9
Bastug G, Eviolitte C, Marko IE (2012) Functionalized orthoesters as powerful building blocks for the efficient preparation of heteroaromatic bicycles. Org Lett 14:3502–3505. doi:10.1021/ol301472a
Tale RH (2002) Novel synthesis of 2- arylbenzothiazoles mediated by ceric ammonium nitrate (CAN). Org Lett 4:1641–1642. doi:10.1021/ol020027i
Karle M, Knecht W, Xue Y (2012) Discovery of benzothiazole guanidines as novel inhibitors of thrombin and trypsin IV. Bioorg Med Chem Lett 22:4839–4843. doi:10.1016/j.bmcl.2012.05.046
Noolvi MN, Patel HM, Kaur M (2012) Benzothiazoles: search for anticancer agents. Eur J Med Chem 54:447–462. doi:10.1016/j.ejmech.2012.05.028
Jaseer EA, Prasad DJC, Dandapat A, Sekar G (2010) An efficient copper(II)-catalyzed synthesis of benzothiazoles through intramolecular coupling-cyclization of \(N\)-(2-chlorophenyl)benzothioamide. Tetrahedron Lett 51:5009–5012. doi:10.1016/j.tetlet.2010.07.079
Xue WJ, Guo YQ, Gao FF, Li HZ, Wu AX (2013) A novel self-sequence reaction network involving a set of six reactions in one pot: the synthesis of substituted benzothiazoles from aromatic ketones and anilines. Org Lett 15:890–893. doi:10.1021/ol400029t
Trapani G, Franco M, Latrofal A, Carotti A, Genchi G, Serra M, Biggio G, Liso G (1996) Synthesis and benzodiazepine receptor binding of some imidazoand pyrimido[2,1-\(b\)]benzothiazoles. Eur J Med Chem 31:575–587. doi:10.1016/0223-5234(96)89553-5
Sahu PK, Sahu PK, Gupta SK, Thavaselvam D, Agarwal DD (2012) Synthesis and evaluation of antimicrobial activity of 4\(H\)-pyrimido[2,1-\(b\)]benzothiazole, pyrazole and benzylidene derivatives of curcumin. Eur J Med Chem 54:366–378. doi: 10.1016/j.ejmech.2012.05.020
Zhu J (2003) Recent developments in the isonitrile-based multicomponent synthesis of heterocycles. Eur J Org Chem 7:1133–1144. doi:10.1002/ejoc.200390167
Domling A (2006) Recent developments in isocyanide-based multicomponent reactions in applied chemistry. Chem Rev 106:17–89. doi:10.1021/cr0505728
Mihovilovic MD, Tanetty P (2007) Metal-assisted multicomponent reactions involving carbon monoxide-towards heterocycle synthesis. Angew Chem Int Ed 46:3612–3615. doi:10.1002/anie.200604743
Chebanov VA, Gura KA, Desenko SM (2010) Aminoazoles as key reagents in multicomponent heterocyclizations. Top Heterocycl Chem 23:41–84. doi:10.1007/7081_2009_21
Sedash YV, Gorobets NY, Chebanov VA, Konovalova IS, Shishkin OV, Desenko SM (2012) Dotting the is in three-component Biginelli-like condensations using 3-amino-1,2,4-triazole as a 1,3-binucleophile. RSC Adv 2:6719–6728. doi:10.1039/C2RA20195J
Wan JP, Liu Y (2010) Synthesis of dihydropyrimidinones and thiones by multicomponent reactions: strategies beyond the classical Biginelli reaction. Synthesis 23:3943–3953. doi:10.1055/s-0030-1258290
Biginelli P (1893) Synthesis of 3,4-dihydropyrimidin-2(1H)-ones. Gazz Chim Ital 23:360–416
Builla AJ, Alajarin R, Jordon P, Vaquero JJ (1995) Synthesis of unsymmetrically substituted 1,4- dihydropyridines and analogous calcium antagonists by microwave heating. Synthesis 4:389–391. doi:10.1055/s-1995-3933
Shaabani A, Rahmati A, Naderi S (2005) A novel one-pot three-component reaction: synthesis of triheterocyclic 4\(H\)-pyrimido[2,1-\(b\)]benzazoles ring systems. Bioorg Med Chem Lett 15:5553. doi:10.1016/j.bmcl.2005.08.101
Tu S, Shao Q, Zhou D, Cao L, Shi F, Li C (2007) Microwave-assisted efficient synthesis of benzo[4,5]imidazo[1,2-a]-pyrimidine derivatives in water under catalyst-free conditions. J Heterocycl Chem 44:1401–1406. doi:10.1002/jhet.5570440625
Sahu PK, Sahu PK, Lal J, Thavaselvam D, Agarwal DD (2012) A facile green synthesis and in vitro antimicrobial activity 4H-pyrimido[2,1-b][1,3]benzothiazole derivatives using aluminum trichloride under solvent free conditions. Med Chem Res 21:3826–3834. doi:10.1007/s00044-011-9908-6
Nagarapu L, Gaikwad HK, Palem JD, Venkatesh R, Bantu R, Sridhar B (2013) Convenient approach for the one-pot, three-component synthesis of triheterocyclic 4H-pyrimido[2,1-b]benzothiazole derivatives using TBAHS. Synth Commun 43:93–104. doi:10.1080/00397911.2011.592624
Sahu PK, Sahu PK, Jain R, Yadava R, Agarwal DD (2012) Hydrotalcite: recyclable, novel heterogeneous catalyst for facile, environmentally benign and high yielding multi-component synthesis and mechanistic study under solvent free conditions. Catal Sci Technol 2:2465–2475. doi:10.1039/c2cy20067h
Rao GBD, Acharya BN, Verma SK, Kaushik MP (2011) N,N-Dichlorobis(2,4,6-trichlorophenyl)urea (CC-2) as a new reagent for the synthesis of pyrimidone and pyrimidine derivatives via Biginelli reaction. Tetrahedron Lett 52:809–812. doi:10.1016/j.tetlet.2010.12.039
Surasani R, Kalita D, Rao AVD, Yarbagi K, Chandrasekhar KB (2012) \(\text{ FeF }_{3}\) as a novel catalyst for the synthesis of polyhydroquinoline derivatives via unsymmetrical Hantzsch reaction. J Fluorine Chem 135:91–96. doi: 10.1016/j.jfluchem.2011.09.005
Atar AB, Jeong YT (2013) Silica supported tungstic acid (STA): an efficient catalyst for the synthesis of bis-spiro piperidine derivatives under milder condition. Tetrahedron Lett 54:1302–1306. doi:10.1016/j.tetlet.2012.12.105
Reddy MV, Reddy CS, Jeong YT (2012) Microwave-assisted, montmorillonite K-10 catalyzed three- component synthesis of \(2H\)-indazolo[2,1-b]phthalazine-triones under solvent-free conditions. Tetrahedron 68:6820–6828. doi:10.1016/j.tet.2012.06.045
Atar AB, Dindulkar SD, Jeong YT (2013) Lithium triflate (LiOTf): a highly efficient and reusable catalytic system for the synthesis of diversified quinolines under neat conditions. Monatsh Chem 144:695–701. doi:10.1007/s00706-012-0906-2
Dindulkar SD, Parthiban P, Jeong YT (2012) \(\text{ BF }_{3}\cdot \text{ SiO }_{2}\) is a simple and efficient Lewis acid catalyst for the one-pot synthesis of polyfunctionalized piperidin-4-ones. Monatsh Chem 143:113–118. doi:10.1007/s00706-011-0576-5
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Atar, A.B., Jeong, Y.T. \(\hbox {FeF}_{3}\) catalyzed cascade C–C and C–N bond formation: synthesis of differentially substituted triheterocyclic benzothiazole functionalities under solvent-free condition. Mol Divers 18, 389–401 (2014). https://doi.org/10.1007/s11030-014-9506-x
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DOI: https://doi.org/10.1007/s11030-014-9506-x