Citation: Chao Wang, Yan-Hong Jiang, Chao-Guo Yan. Convenient synthesis of spiro[indoline-3,4'-pyrano[2,3-c]pyrazole] and spiro[acenaphthyl-3,4'-pyrano[2,3-c]pyrazoles] via fourcomponent reaction[J]. Chinese Chemical Letters, ;2015, 26(7): 889-893. doi: 10.1016/j.cclet.2015.05.018 shu

Convenient synthesis of spiro[indoline-3,4'-pyrano[2,3-c]pyrazole] and spiro[acenaphthyl-3,4'-pyrano[2,3-c]pyrazoles] via fourcomponent reaction

1.
College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, China

Corresponding author: Chao-Guo Yan,
Received Date: 3 March 2015
Available Online: 6 April 2015
Fund Project: This work was financially supported by the National Natural Science Foundation of China (No. 21172189) (No. 21172189)

The domino four-component reaction of hydrated hydrazine, dimethyl acetylenedicarboxylate, isatin and malononitrile or ethyl cycanoacetate in ethanol in the presence of triethylamine afforded the polysubstituted spiro[indoline-3,4'-pyrano[2,3-c]pyrazole] derivatives in satisfactory yields. Under similar conditions, the four-component reaction containing acenaphthenequinone also resulted in the spiro[acenaphthyl-3,4'-pyrano[2,3-c]pyrazole] in good yields.
- Multicomponent reaction,
- Spirooxindole,
- Pyrano[2,3-c]pyrazole,
- Isatin,
- Acenaphthenequinone
1. [1]
  [1] A.H. Abdel-Rahman, E.M. Keshk, M.A. Hanna, S.M. El-Bady, Synthesis and evaluation of some new spiro indoline-based heterocycles as potentially active antimicrobial agents, Bioorg. Med. Chem. 12 (2004) 2483–2488.
2. [2]
  [2] M.A. Koch, A. Schuffenhauer, M. Scheck, et al., Charting biologically relevant chemical space: a structural classification of natural products, Proc. Natl. Acad. Sci. U.S.A. 102 (2005) 17272–17277.
3. [3]
  [3] G.S. Singh, Z.Y. Desta, Isatins as privileged molecules in design and synthesis of spiro-fused cyclic frameworks, Chem. Rev. 112 (2012) 6104–6155.
4. [4]
  [4] B.M. Trost, M.K. Brennan, Asymmetric syntheses of oxindole and indole spirocyclic alkaloid natural products, Synthesis 18 (2009) 3003–3025.
5. [5]
  [5] N.R. Ball-Jones, J.J. Badillo, A.K. Franz, Strategies for the enantioselective synthesis of spirooxindoles, Org. Biomol. Chem. 10 (2012) 5165–5181.
6. [6]
  [6] L. Hong, R. Wang, Recent advances in asymmetric organocatalytic construction of 3,3'-spirocyclic oxindoles, Adv. Synth. Catal. 355 (2013) 1023–1030.
7. [7]
  [7] B. Tan, N.R. Candeias, C.F. Barbas III, Construction of bispirooxindoles containing three quaternary stereocenters in a cascade using a single multifunctional organocatalyst, Nat. Chem. 3 (2011) 473–4776.
8. [8]
  [8] F. Shi, Z.L. Tao, S.W. Luo, S.J. Tu, L.Z. Gong, Scaffold-inspired enantioselective synthesis of biologically important spiro[pyrrolidin-3,20-oxindoles] with structural diversity through catalytic isatin-derived 1,3-dipolar cycloadditions, Chem. Eur. J. 18 (2012) 6885–6894.
9. [9]
  [9] H. Deng, Y. Wei, M. Shi, Highly regio- and diastereoselective construction of spirocyclopenteneoxindoles through phosphine-catalyzed [3 + 2] annulation of Morita-Baylis-Hillman carbonates with isatylidene malononitriles, Org. Lett. 13 (2011) 3348–3351.
10. [10]
  [10] X. Li, Y. Li, F. Peng, et al., Highly enantioselective one-pot synthesis of spirocyclopentaneoxindoles containing the oxime group by organocatalyzed michael addition/ISOC/fragmentation sequence, Org. Lett. 13 (2011) 6160–6163.
11. [11]
  [11] S.C. Kuo, L.J. Huang, H. Nakamura, Studies on heterocyclic compounds. 6. Synthesis and analgesic and antiinflammatory activities of 3,4-dimethylpyrano[2,3- c]pyrazol-6-one derivatives, J. Med. Chem. 17 (1984) 539–544.
12. [12]
  [12] J.L. Wang, D. Liu, Z.J. Zheng, et al., Structure-based discovery of an organic compound that binds Bcl-2 protein and induces apoptosis of tumor cells, Proc. Natl. Acad. Sci. U.S.A. 97 (2000) 7124–7129.
13. [13]
  [13] V.D. Dyachenko, E.B. Rusanov, Novel approaches to synthesis of 4-alkyl-6-amino- 5-cyano-3-methyl(propyl, phenyl)-2H,4H-pyrano[2,3-c]pyrazoles, Chem. Heterocycl. Compd. 40 (2004) 231–240.
14. [14]
  [14] A. Shaabani, E. Soleimani, A. Sarvary, A.H. Rezayan, A simple and efficient approach to the synthesis of 4H-furo[3,4-b]pyrans via a three-component reaction of isocyanides, Bioorg. Med. Chem. Lett. 18 (2008) 3968–3970.
15. [15]
  [15] A. Shaabani, A. Sarvary, A.H. Rezayan, S. Keshipour, Synthesis of fully substituted pyrano[2,3-c]pyrazole derivatives via a multicomponent reaction of isocyanides, Tetrahedron 65 (2009) 3492–3495.
16. [16]
  [16] Y.M. Litvinov, A.A. Shestopalov, L.A. Rodinovskaya, A.M. Shestopalov, New convenient four-component synthesis of 6-amino-2,4-dihydropyrano[2,3-c]pyrazol- 5-carbonitriles and one-pot synthesis of 6'-aminospiro[(3H)-indol-3,4'-pyrano[2,3-c]pyrazol]-(1H)-2-on-5'-carbonitriles, J. Comb. Chem. 11 (2009) 914–919.
17. [17]
  [17] H.M. Al-Matar, K.D. Khalil, A.Y. Adam, M.H. Elnagdi, Green one pot solvent-free synthesis of pyrano[2,3-c]-pyrazoles and pyrazolo[1,5-a]pyrimidines, Molecules 15 (2010) 6619–6629.
18. [18]
  [18] K. Kanagaraj, K. Pitchumani, Solvent-free multicomponent synthesis of pyranopyrazoles; per-6-amino-β-cyclodextrin as a remarkable catalyst and host, Tetrahedron Lett. 51 (2010) 3312–3316.
19. [19]
  [19] H. Mecadon, M.D.R. Rohman, I. Kharbangar, et al., L-Proline as an efficient catalyst for the multi-component synthesis of 6-amino-4-alkyl/aryl-3-methyl-2,4-dihydropyrano[ 2,3-c]pyrazole-5-carbonitriles in water, Tetrahedron Lett. 52 (2011) 3228–3231.
20. [20]
  [20] S. Muramulla, C.G. Zhao, A new catalytic mode of the modularly designed organocatalysts (MDOs): enantioselective synthesis of dihydropyrano[2,3-c]pyrazoles, Tetrahedron Lett. 52 (2011) 3905–3908.
21. [21]
  [21] A.M. Shestopalov, Y.M. Emeliyanova, A.A. Shestopalov, et al., Cross-condensation of derivatives of cyanoacetic acid and carbonyl compounds. Part 1: single-stage synthesis of 10-substituted 6-amino-spiro-4-(piperidine-4')-2H,4H-pyrano[2,3-c]pyrazole-5-carbonitriles, Tetrahedron 59 (2003) 7491–7496.
22. [22]
  [22] G. Vasuki, K. Kumaravel, Rapid four-component reactions in water: synthesis of pyranopyrazoles, Tetrahedron Lett. 49 (2008) 5636–5638.
23. [23]
  [23] S. Gogoi, C.G. Zhao, Organocatalyzed enantioselective synthesis of 6-amino-5- cyanodihydropyrano[2,3-c]pyrazoles, Tetrahedron Lett. 50 (2009) 2252–2255.
24. [24]
  [24] A. Siddekha, A. Nizam, M.A. Pasha, An efficient and simple approach for the synthesis of pyranopyrazoles using imidazole (catalytic) in aqueous medium, and the vibrational spectroscopic studies on 6-amino-4-(4'-methoxyphenyl)-5-cyano- 3-methyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazole using density functional theory, Spectrochim. Acta A 81 (2011) 431–440.
25. [25]
  [25] H. Mecadon, M.R. Rohman, M. Rajbangshi, B. Myrboh, γ-Alumina as a recyclable catalyst for the four-component synthesis of 6-amino-4-alkyl/aryl-3-methyl-2,4- dihydropyrano[2,3-c]pyrazole-5-carbonitriles in aqueous medium, Tetrahedron Lett. 52 (2011) 2523–2525.
26. [26]
  [26] H. Mecadon, M.R. Rohman, I. Kharbangar, et al., L-Proline as an efficient catalyst for the multi-component synthesis of 6-amino-4-alkyl/aryl-3-methyl-2,4-dihydropyrano[ 2,3-c]pyrazole-5-carbonitriles in water, Tetrahedron Lett. 52 (2011) 3228–3231.
27. [27]
  [27] S.H.S. Azzam, M.A. Pasha, Simple and efficient protocol for the synthesis of novel dihydro-1H-pyrano[2,3-c]pyrazol-6-ones via a one-pot four-component reaction, Tetrahedron Lett. 53 (2012) 6834–6837.
28. [28]
  [28] S.R. Mandha, S. Siliveri, M. Alla, et al., Eco-friendly synthesis and biological evaluation of substituted pyrano[2,3-c]pyrazoles, Bioorg. Med. Chem. Lett. 22 (2012) 5272–5278.
29. [29]
  [29] A.M. Zonouz, I. Eskandari, H.R. Khavasi, A green and convenient approach for the synthesis of methyl 6-amino-5-cyano-4-aryl-2,4-dihydropyrano[2,3-c]pyrazole- 3-carboxylates via a one-pot, multi-component reaction in water, Tetrahedron Lett. 53 (2012) 5519–5522.
30. [30]
  [30] J. Albadi, A. Mansournezhad, Z. Derakhshandeh, CuO-CeO₂ nanocomposite: a highly efficient recyclable catalyst for the multicomponent synthesis of 4Hbenzo[ b]pyran derivatives, Chin. Chem. Lett. 24 (2013) 821–824.
31. [31]
  [31] J.X. Yu, Y.B. Zhou, T.H. Shen, et al., Novel and efficient one-pot synthesis of spiro[indoline-3,4'-pyrano[2,3-c]pyrazole]derivatives catalyzed by L-proline in aqueous medium, J. Chem. Res. 37 (2013) 365–368.
32. [32]
  [32] S. Pal, M.D. Khan, S. Karamthulla, S.J. Abbas, L.H. Choudhury, One pot fourcomponent reaction for the efficient synthesis of spiro[indoline-3,40-pyrano[2,3-c]pyrazole]-30-carboxylate derivatives, Tetrahedron Lett. 54 (2013) 5434–5440.
33. [33]
  [33] Y. Zou, Y. Hu, H. Liu, D.Q. Shi, Rapid and efficient ultrasound-assisted method for the combinatorial synthesis of spiro[indoline-3,4'-pyrano[2,3-c]pyrazole] derivatives, ACS Comb. Sci. 14 (2012) 38–43.
34. [34]
  [34] S. Ahadi, Z. Yasaei, A. Bazgir, A clean and one-pot synthesis of spiroindolinepyranopyrazoles, J. Heterocycl. Chem. 47 (2010) 1090–1094.
35. [35]
  [35] X.Q. Liu, X.L. Xu, X. Wang, et al., A facile and convenient way to functionalized trifluoromethylated spirocyclic[indole-3,4-pyrano[2,3-c]pyrazole] derivatives, Tetrahedron Lett. 54 (2013) 4451–4455.
36. [36]
  [36] Y. Sun, Q. Wu, L.J. Zhang, C.G. Yan, Efficient synthesis of the functionalized spiro[indoline-3,4'-pyridine] via four-component reaction, Chin. J. Chem. 30 (2012) 1548–1554.
37. [37]
  [37] Y. Sun, J. Sun, C.G. Yan, Synthesis of 10-aryl-2'-(2-oxoindolin-3-yl)spiro[indoline- 3,5'-pyrroline]-2,3'-dione via one-pot reaction of arylamines, acetone, and isatins, Tetrahedron Lett. 53 (2012) 3647–3649.
38. [38]
  [38] Y. Han, Q. Wu, J. Sun, C.G. Yan, Synthesis of the functionalized spiro[indoline-3,5'-pyrroline]-2,2'-diones via three-component reactions of arylamines, acetylenedicarboxylates, and isatins, Tetrahedron 68 (2012) 8539–8544.
39. [39]
  [39] J. Sun, Y. Sun, H. Gao, C.G. Yan, Synthesis of spiro[indoline-3,2'-quinoline] derivatives through a four-component reaction, Eur. J. Org. Chem. 10 (2012) 1976–1983.
40. [40]
  [40] L. Wu, J. Sun, C.G. Yan, Facile synthesis of spiro[indoline-3,3'-pyrrolo[1,2-a]quinolines] and spiro[indoline-3,1'-pyrrolo[2,1-a]isoquinolines] via 1,3-dipolar cycloaddition reactions of heteroaromatic ammonium salts with 3-phenacylideneoxindoles, Org. Biomol. Chem. 10 (2012) 9452–9463.
41. [41]
  [41] J. Sun, Y. Sun, H. Gong, Y.J. Xue, C.G. Yan, Synthesis of spiro[dihydropyridineoxindoles] via three-component reaction of arylamine, isatin and cyclopentane-1,3-dione, Beilstein J. Org. Chem. 9 (2013) 8–14.
42. [42]
  [42] D.M. Pore, P.B. Patil, D.S. Gaikwad, et al., Green access to novel spiro pyranopyrazole derivatives, Tetrahedron Lett. 54 (2013) 5876–5878.
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