Citation: Hamzeh Kiyani, Maryam Ghiasi. Potassium phthalimide: An efficient and green organocatalyst for the synthesis of 4-aryl-7-(arylmethylene)-3, 4, 6, 7-tetrahydro-1Hcyclopenta[d]pyrimidin-2(5H)-ones/thiones under solvent-free conditions[J]. Chinese Chemical Letters, ;2014, 25(2): 313-316. shu

Potassium phthalimide: An efficient and green organocatalyst for the synthesis of 4-aryl-7-(arylmethylene)-3, 4, 6, 7-tetrahydro-1Hcyclopenta[d]pyrimidin-2(5H)-ones/thiones under solvent-free conditions

Hamzeh Kiyani ^, ,
Maryam Ghiasi

1.
School of Chemistry, Damghan University, Damghan 36715-365, Iran

Corresponding author: Hamzeh Kiyani,
Received Date: 11 July 2013
Available Online: 6 November 2013

An efficient synthesis of Biginelli-type compounds using potassium phthalimide as a green, mild, and commercially available organocatalyst in a one-pot, multi-component cyclocondensation reaction of cyclopentanone, aldehydes, and urea/thiourea is reported. The present methodology is a green approach to access 4-aryl-7-(arylmethylene)-3,4,6,7-tetrahydro-1H-cyclopenta[d]pyrimidin-2(5H)-ones/thiones. It offers several merits such as simple operational procedures, no use of hazardous organic solvents, and cheap and environmentally friendly solid basic catalyst.
- Organocatalyst,
- Potassium phthalimide,
- Biginelli reaction,
- Pyrimidinone,
- Solvent-free
1. [1]
  [1] T.U. Mayer, T.M. Kapoor, S.J. Haggarty, et al., Small molecule inhibitor of mitotic spindle bipolarity identified in a phenotype-based screen, Science 286 (1999) 971-974.
2. [2]
  [2] Z. Maliga, T.M. Kapoor, T.J. Mitchison, Evidence that monastrol is an allosteric inhibitor of the mitotic kinesin Eg5, Chem. Biol. 9 (2002) 989-996.
3. [3]
  [3] J.C. Barrow, P.G. Nantermet, H.G. Selnick, et al., In vitro and in vivo evaluation of dihydropyrimidinone C-5 amides as potent and selective alpha1A receptor antagonists for the treatment of benign prostatic hyperplasia, J. Med. Chem. 43 (2000) 2703-2718.
4. [4]
  [4] C. Goldstein, J.C. Schroeder, J.P. Fortin, et al., Two naturally occurring mutations in the type 1 melanin-concentrating hormone receptor abolish agonist-induced signaling, J. Pharm. Exp. Ther. 335 (2010) 799-806.
5. [5]
  [5] K.S. Atwal, B.N. Swanson, S.E. Unger, et al., Dihydropyrimidine calcium channel blockers. 3,3-carbamoyl-4-aryl-1,2,3,4-tetrahydro-6-methyl-5-pyrimidinecarbox- ylic acid esters as orally effective antihypertensive agents, J. Med. Chem. 34 (1991) 806-811.
6. [6]
  [6] M. Matache, C. Dobrota, N.D. Bogdan, et al., Synthesis of fused dihydro-pyrimido[4, 3-d]coumarins using Biginelli multicomponent reaction as key step, Tetrahedron 65 (2009) 5949-5957.
7. [7]
  [7] Y.X. Da, Z. Zhang, Z.J. Quan, Intermolecular cyclocondensation reaction of 3,4- dihydropyrimidine-2-thione under the Mitsunobu reaction conditions, Chin. Chem. Lett. 22 (2011) 679-682.
8. [8]
  [8] T.N. Akhaja, J.P. Raval, Design, synthesis, in vitro evaluation of tetrahydropyrimidine- isatin hybrids as potential antibacterial, antifungal and anti-tubercular agents, Chin. Chem. Lett. 23 (2012) 446-449.
9. [9]
  [9] A. Ghorbani-Choghamarani, P. Zamani, Three component reactions: An efficient and green synthesis of 3, 4-dihydropyrimidin-2-(1H)-ones and thiones using silica gel-supported l-pyrrolidine-2-carboxylic acid-4-hydrogen sulfate, Chin. Chem. Lett. 24 (2013) 804-808.
10. [10]
  [10] S. Rostamnia, K. Lamei, Diketene-based neat four-component synthesis of the dihydropyrimidinones and dihydropyridine backbones using silica sulfuric acid (SSA), Chin. Chem. Lett. 23 (2012) 930-932.
11. [11]
  [11] M.M. Heravi, N. Karimi, H. Hamidi, et al., Cu/SiO₂: a recyclable catalyst for the synthesis of octahydroquinazolinone, Chin. Chem. Lett. 24 (2013) 143-144.
12. [12]
  [12] C.O. Kappe, 100 years of the Biginelli dihydropyrimidine synthesis, Tetrahedron 49 (1993) 6937-6963.
13. [13]
  [13] C.O. Kappe, Recent advances in the Biginelli dihydropyrimidine synthesis. New tricks from an old dog, Acc. Chem. Res. 33 (2000) 879-888.
14. [14]
  [14] C.O. Kappe, Biologically active dihydropyrimidones of the Biginelli-type-a literature survey, Eur. J. Med. Chem. 35 (2000) 1043-1052.
15. [15]
  [15] K.S. Atwal, G.C. Rovnyak, S.D. Kimball, et al., Dihydropyrimidine calcium channel blockers. 2, 3-substituted-4-aryl-1,4-dihydro-6-methyl-5-pyrimidinecarboxylic acid esters as potent mimics of dihydropyridines, J.Med. Chem. 33 (1990) 2629-2635.
16. [16]
  [16] H.I. El-Subbagh, S.M. Abu-Zaid, M.A. Mahran, F.A. Badria, A.M. Al-Obaid, Synthesis and biological evaluation of certain a, b-unsaturated ketones and their corresponding fused pyridines as antiviral and cytotoxic agents, J. Med. Chem. 43 (2000) 2915-2921.
17. [17]
  [17] Y.L. Zhu, S.L. Huang, Y.J. Pan, Highly chemoselective multi-component Biginellitype condensations of cycloalkanones, urea or thiourea and aldehydes, Eur. J. Org. Chem. 2005 (2005) 2354-2367.
18. [18]
  [18] M. Hong, C. Cai, Three-component one-pot synthesis of pyrimidinone derivatives in fluorous media: ytterbium bis(perfluorooctanesulfonyl)imide complex catalyzed Biginelli-type reaction, J. Heterocycl. Chem. 46 (2009) 1430-1432.
19. [19]
  [19] N.T.A. Dawoud, An efficient and environmentally friendly procedure for synthesis of quinazolinone derivatives by use of a Biginelli-type reaction, Chem. Sci. Trans. 2 (2013) 129-134.
20. [20]
  [20] H.H. Zhang, Z.Q. Zhou, Z.G. Yao, F. Xu, Q. Shen, Efficient synthesis of pyrimidinone derivatives by ytterbium chloride catalyzed Biginelli-type reaction under solventfree conditions, Tetrahedron Lett. 50 (2009) 1622-1624.
21. [21]
  [21] A.R. Hajipour, Y. Ghayeb, N. Sheikhan, A.E. Ruoho, Brønsted acidic ionic liquid as an efficient and reusable catalyst for one-pot, three-component synthesis of pyrimidinone derivatives via Biginelli-type reaction under solvent-free conditions, Synth. Commun. 41 (2011) 2226-2233.
22. [22]
  [22] M. Rahman, A. Majee, A. Hajra, Microwave-assisted Brønsted acidic ionic liquidpromoted one-pot synthesis of heterobicyclic dihydropyrimidinones by a threecomponent coupling of cyclopentanone, aldehydes, and urea, J. Heterocycl. Chem. 47 (2010) 1230-1233.
23. [23]
  [23] M. Lei, L. Ma, L.H. Hu, An efficient and environmentally friendly procedure for synthesis of pyrimidinone derivatives by use of a Biginelli-type reaction, Monatsh. Chem. 141 (2010) 1005-1008.
24. [24]
  [24] M.I. Ali, A. El-Fotooh, G. Hammam, Reactions with (arylmethylene)cycloalkanones, 1,2,6-bis(arylmethylene)cyclohexanenes, J. Chem. Eng. Data 23 (1978) 351-352.
25. [25]
  [25] G.E.H. Elgemeie, A.M.E. Attia, S.S. Alkabai, Nucleic acid components and their analogues: new synthesis of bicyclic thiopyrimidine nucleosides, Nucleos. Nucleot. Nucl. 19 (2000) 723-734.
26. [26]
  [26] M.I. Ali, A. El-Fotooh, G. Hammam, N.M. Youssef, Reactions with (arylmethylene) cycloalkanones, 3,synthesis of 11-(arylmethylene)octahydrocycloocta[d]thiazolo[3,2-a]pyrimidin-3-one derivatives of expected biological activity, J. Chem. Eng. Data 26 (1981) 214-215.
27. [27]
  [27] M.A. Al-Omar, K.M. Youssef, M.A. El-Sherbeny, S.A.A. Awadalla, H.I. El-Subbagh, Synthesis and in vitro antioxidant activity of some new fused pyridine analogs, Arch. Pharm. Chem. Life Sci. 338 (2005) 175-180.
28. [28]
  [28] S.M. Rajesh, R.S. Kumar, L.A. Libertsen, et al., A green expedient synthesis of pyridopyrimidine-2-thiones and their antitubercular activity, Bioorg. Med. Chem. Lett. 21 (2011) 3012-3016.
29. [29]
  [29] Z.L. Shen, X.P. Xu, S.J. Ji, Brønsted base-catalyzed one-pot three-component Biginelli-type reaction: an efficient synthesis of 4,5,6-triaryl-3,4-dihydropyrimidin- 2(1H)-one and mechanistic study, J. Org. Chem. 75 (2010) 1162-1167.
30. [30]
  [30] F. Tamaddon, Z. Razmi, A.A. Jafari, Synthesis of 3,4-dihydropyrimidin-2(1H)-ones and 1,4-dihydropyridines using ammonium carbonate in water, Tetrahedron Lett. 51 (2010) 1187-1189.
31. [31]
  [31] J.O. Metzger, Solvent-free organic syntheses, Angew. Chem. Int. Ed. 37 (1998) 2975-2978.
32. [32]
  [32] M.S. Singh, S. Chowdhury, Recent developments in solvent-free multicomponent reactions: a perfect synergy for eco-compatible organic synthesis, RSC Adv. 2 (2012) 4547-4592.
33. [33]
  [33] K.Tanaka, F.Toda, Solvent-free organic synthesis,Chem. Rev.100 (2000)1025-1074.
34. [34]
  [34] M.J. Climent, A. Corma, S. Iborra, Homogeneous and heterogeneous catalysts for multicomponent reactions, RSC Adv. 2 (2012) 16-58.
35. [35]
  [35] L. Chen, J. Zhao, S.F. Yin, C.T. Au, A mini-review on solid superbase catalysts developed in the past two decades, RSC Adv. 3 (2013) 3799-3814.
36. [36]
  [36] M.J. Climent, A. Corma, S.B.A. Hamid, S. Iborra, M. Mifsud, Chemicals from biomass derived products: synthesis of polyoxyethyleneglycol esters from fatty acid methyl esters with solid basic catalysts, Green Chem. 8 (2006) 524-532.
37. [37]
  [37] P.L. Salzberg, J.V. Supniewski, in: H. Gilman, A.H. Blatt (Eds.), Organic Synthesis Collection, 1, John Wiley, New York, 1995, p. 119.
38. [38]
  [38] M.B. Smith, J. March, March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 5th ed., John Wiley, New York, 2001.
39. [39]
  [39] S.H. Chan, K.H. Lam, C.H. Chui, et al., The preparation and in vitro antiproliferative activity of phthalimide based ketones on MDAMB-231 and SKHep-1 human carcinoma cell lines, Eur. J. Med. Chem. 44 (2009) 2736-2740.
40. [40]
  [40] P. Singh, S. Kaur, S. Kumar, et al., Synthesis and in vitro cytotoxic evaluation of Nalkylbromo and N-alkylphthalimido-isatins, Bioorg. Med. Chem. Lett. 21 (2011) 3017-3020.
41. [41]
  [41] C.I. Manley-King, J.J. Bergh, J.P. Petzer, Inhibition of monoamine oxidase by C5- substituted phthalimide analogues, Bioorg. Med. Chem. 19 (2011) 4829-4840.
42. [42]
  [42] M.G. Dekamin, Z. Karimi, Activation of trimethylsilyl cyanide by potassium phthalimide for facile synthesis of TMS-protected cyanohydrins, J. Organomet. Chem. 694 (2009) 1789-1794.
43. [43]
  [43] M.G. Dekamin, S. Sagheb-Asl, M.R. Naimi-Jamal, An expeditious synthesis of cyanohydrin trimethylsilyl ethers using tetraethylammonium 2-(carbamoyl)benzoate as a bifunctional organocatalyst, Tetrahedron Lett. 50 (2009) 4063-4066.
44. [44]
  [44] A. Amoozadeh, S. Rahmani, F. Nemati, Poly(ethylene)glycol/AlCl3 as a new and efficient system for multicomponent Biginelli-type synthesis of pyrimidinone derivatives, Heterocycl. Commun. 19 (2013) 69-73.
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