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FeF3-mediated tandem annulation: a highly efficient one-pot synthesis of functionalized N-methyl-3-nitro-4H-pyrimido [2, 1-b] [1, 3] benzothiazole-2-amine derivatives under neat conditions

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Abstract

A straight forward and highly efficient one-pot annulation of 2-aminobenzothiazole, (E)-N-methyl-1-(methylthio)-2-nitroethenamine, and aldehydes in the presence of FeF3 is described. Diverse functionalized N-methyl-3-nitro-4H-pyrimido [2, 1-b] [1, 3] benzothiazole-2-amine derivatives were obtained with excellent yields under neat conditions. The one-pot annulation was shown to be valid for the synthesis of highly functionalized derivatives of N-methyl-3-nitro-4H-pyrimido [2, 1-b] [1, 3] benzothiazole-2-amine from readily accessible substrates. The catalyst FeF3 can be easily recovered and reused for the next reaction without any effects on the yields of the products. This green protocol provides structurally complex, biologically important N-methyl-3-nitro-4H-pyrimido [2, 1-b] [1, 3] benzothiazole-2-amine in a one-pot operation.

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Fig. 1
Scheme 1
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References

  1. Tietze LF (1996) Domino reactions in organic synthesis. Chem Rev 96:115–136. https://doi.org/10.1021/cr950027e

    Article  CAS  PubMed  Google Scholar 

  2. Tietze LF (2014) Domino reactions: concepts for efficient organic synthesis. Wiley, Weinheim. https://doi.org/10.1002/9783527671304

    Book  Google Scholar 

  3. Dömling A (2006) Recent developments in isocyanide based multicomponent reactions in applied chemistry. Chem Rev 106:17–89. https://doi.org/10.1021/cr0505728

    Article  CAS  PubMed  Google Scholar 

  4. Alvarez-Rodríguez NV, Islas-Jácome A, Rentería-Gómez A, Cárdenas-Galindo LE, Unnamatla MVB, Gámez-Montaño R (2018) Synthesis of 1′-tetrazolylmethyl-spiro[pyrrolidine-3,3′-oxindoles] via two coupled one-pot processes Ugi-azide/Pictet–Spengler and oxidative spiro-rearrangement. New J Chem 42:1600–1603. https://doi.org/10.1039/c7nj03829a

    Article  CAS  Google Scholar 

  5. Bandara N, Sharma AK, Krieger S, Schultz JW, Han BH, Rogers BE, Mirica LM (2017) Evaluation of 64Cu-based radiopharmaceuticals that target Aβ peptide aggregates as diagnostic tools for alzheimer’s disease. J Am Chem Soc 139:12550–12558. https://doi.org/10.1021/jacs.7b05937

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  6. Venugopala KN, Krishnappa M, Nayak SK, Subrahmanya BK, Vaderapura JP, Chalannavar RK, Gleiser RM, Odhav B (2013) Synthesis and antimosquito properties of 2,6-substituted benzo[d]thiazole and 2,4-substituted benzo[d]thiazole analogues against Anopheles arabiensis. Eur J Med Chem 65:295–303. https://doi.org/10.1016/j.ejmech.2013.04.061

    Article  CAS  PubMed  Google Scholar 

  7. Ugale VG, Patel HM, Wadodkar SG, Bari SB, Shirkhedkar AA, Surana S (2012) Quinazolino–benzothiazoles: fused pharmacophores as anticonvulsant agents. J Eur J Med Chem 53:107–113. https://doi.org/10.1016/j.ejmech.2012.03.045

    Article  CAS  Google Scholar 

  8. Sarkar S, Dwivedi J, Chauhan R (2013) Synthesis of 1-[2 (substituted phenyl)-4-oxothiazolidin-3-yl]-3-(6-fluro-7-chloro-1, 3-benzothiazol-2-yl)-ureas as anthelmintic agent. J Pharm Res 7:439–442. https://doi.org/10.1016/j.jopr.2013.05.008

    Article  CAS  Google Scholar 

  9. Cai J, Sun M, Wu X, Chen J, Wang P, Zong X, Ji M (2013) Design and synthesis of novel 4-benzothiazole amino quinazolines Dasatinib derivatives as potential anti-tumor agents. Eur J Med Chem 63:702–712. https://doi.org/10.1016/j.ejmech.2013.03.013

    Article  CAS  PubMed  Google Scholar 

  10. Yoshida M, Hayakawa I, Hayashi N, Agatsuma T, Oda Y, Tanzawa F, Iwasaki S, Koyama K, Furukawa H, Kurakata S, Sugano Y (2005) Synthesis and biological evaluation of benzothiazole derivatives as potent antitumor agents. Bioorg Med Chem Lett 15:3328–3332. https://doi.org/10.1016/j.bmcl.2005.05.077

    Article  CAS  PubMed  Google Scholar 

  11. Noël S, Cadet S, Gras E, Hureau C (2013) The benzazole scaffold: a SWAT to combat Alzheimer’s disease. Chem Soc Rev 42:7747–7762. https://doi.org/10.1039/C3CS60086F

    Article  PubMed  Google Scholar 

  12. Prajapati NP, Vekariya RH, Borad MA, Patel HD (2014) Recent advances in the synthesis of 2-substituted benzothiazoles: a review. RSC Adv 4:60176–60208. https://doi.org/10.1039/C4RA07437H

    Article  CAS  Google Scholar 

  13. Mako TL, Byers JA (2016) Recent advances in iron-catalysed cross coupling reactions and their mechanistic underpinning. Inorg Chem Front 3:766–790. https://doi.org/10.1039/C5QI00295H

    Article  CAS  Google Scholar 

  14. Shang R, Ilies L, Nakamura E (2017) Iron-catalyzed C-H bond activation. Chem Rev 117:9086–9139. https://doi.org/10.1021/acs.chemrev.6b00772

    Article  CAS  PubMed  Google Scholar 

  15. Tang J, Yang M, Wang J, Dong W, Wang G (2015) Heterogeneous Fe-MIL-101 catalysts for efficient one-pot four-component coupling synthesis of highly substituted pyrroles. New J Chem 39:4919–4923. https://doi.org/10.1039/C5NJ00632E

    Article  CAS  Google Scholar 

  16. Bandgar BP, Kamble VT, Kulkarni A (2005) Iron (iii) fluoride: a highly efficient and versatile catalyst for the protection of carbonyl compounds under solvent-free conditions. Aust J Chem 58:607–610. https://doi.org/10.1071/CH05067

    Article  CAS  Google Scholar 

  17. Bhaskar KT, Sumanth C, Dhanunjaya RAV, Kalita D, Srinivasa RM, Chandra SKB, Shiva KK, Pal M (2012) Catalysis by FeF3 in water: a green synthesis of 2-substituted 1, 3-benzazoles and 1, 2-disubstituted benzimidazoles. RSC Adv 2:11510–11519. https://doi.org/10.1039/C2RA22302C

    Article  Google Scholar 

  18. Surasani RK, Rao AVD, Yarbagi K, Chandrasekhar KB (2012) FeF3 as a novel catalyst for the synthesis of polyhydroquinoline derivatives via unsymmetrical Hantzsch reaction. J Fluor Chem 135:91–96. https://doi.org/10.1016/j.jfluchem.2011.09.005

    Article  CAS  Google Scholar 

  19. Atar AB, Jeong YS, Jeong YT (2014) Iron fluoride: the most efficient catalyst for one-pot synthesis of 4H-pyrimido [2, 1-b] benzothiazoles under solvent-free conditions. Tetrahedron 70:5207–5213. https://doi.org/10.1016/j.tet.2014.05.094

    Article  CAS  Google Scholar 

  20. 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. https://doi.org/10.1016/j.tetlet.2012.12.105

    Article  CAS  Google Scholar 

  21. Atar AB, Jeong YT (2013) Heterogenized tungsten complex: an efficient and high yielding catalyst for the synthesis of structurally diverse tetra substituted pyrrole derivatives via four-component assembly. Tetrahedron Lett 54:5624–5628. https://doi.org/10.1016/j.tetlet.2013.08.016

    Article  CAS  Google Scholar 

  22. Atar AB, Kim JS, Lim KT, Jeong YT (2015) Bridging homogeneous and heterogeneous catalysis with CAN·SiO2 as a solid catalyst for four-component reactions for the synthesis of tetrasubstituted pyrroles. New J Chem 39:396–402. https://doi.org/10.1039/C4NJ01234H

    Article  CAS  Google Scholar 

  23. Atar AB, Kim JT, Lim KT, Jeong YT (2014) Synthesis of 6-Amino-2, 4-dihydropyrano [2, 3-c] pyrazol-5-carbonitriles catalyzed by silica-supported tetramethylguanidine under solvent-free conditions. Synth Commun 44:2679–2691. https://doi.org/10.1080/00397911.2014.913634

    Article  CAS  Google Scholar 

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Acknowledgements

This research was supported by Basic Science Research Program through the National Research Foundation of Republic of Korea (NRF) funded by the Ministry of Education, Science and Technology (2016R1D1A1B01007177).

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  1. Department of Chemistry, Sejong University, Seoul, 143-747, South Korea

    Amol Balu Atar, Eunbi Han & Jongmin Kang

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  1. Amol Balu Atar
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  2. Eunbi Han
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  3. Jongmin Kang
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Correspondence to Amol Balu Atar or Jongmin Kang.

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Atar, A.B., Han, E. & Kang, J. FeF3-mediated tandem annulation: a highly efficient one-pot synthesis of functionalized N-methyl-3-nitro-4H-pyrimido [2, 1-b] [1, 3] benzothiazole-2-amine derivatives under neat conditions. Mol Divers 24, 443–453 (2020). https://doi.org/10.1007/s11030-019-09963-2

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