Citation: Govindaraju Santhosh, Tabassum Sumaiya, Khan Riyaz-ur-Rahaman, Afzal Pasha Mohamed. Meglumine catalyzed one-pot green synthesis of novel 4,7-dihydro-1H-pyrazolo[3,4-b]pyridin-6-amines[J]. Chinese Chemical Letters, ;2017, 28(2): 437-441. doi: 10.1016/j.cclet.2016.09.013 shu

Meglumine catalyzed one-pot green synthesis of novel 4,7-dihydro-1H-pyrazolo[3,4-b]pyridin-6-amines

Department of Studies in Chemistry, Central College Campus, Bangalore University, Bengaluru 560001, India

Corresponding author: Afzal Pasha Mohamed, m_af_pasha@ymail.com
Received Date: 12 June 2016
Revised Date: 26 August 2016
Accepted Date: 26 August 2016
Available Online: 21 February 2016

Figures(2)

Meglumine efficiently catalyzes the one-pot, five-component reaction of hydrazine, ethyl acetoacetate, aryl aldehydes, substituted phenylacetonitriles and ammonium acetate in ethanol at room temperature to afford novel 4,7-dihydro-1H-pyrazolo[3,4-b]pyridin-6-amine derivatives. The present approach offers several advantages such as shorter reaction durations, low cost, excellent yields, milder reaction conditions, simple workup procedure and is environment friendly. All the synthesized derivatives are characterized by IR, ¹H NMR, ¹³C NMR, HRMS and CHN analysis.
- One-pot five-component reaction,
- Substituted phenylacetonitriles,
- Meglumine,
- Pyrazolopyridin-6-amines,
- Ethanol
1. [1]
  (a) J. Zhu, H. Bienaymé, Multicomponent Reactions, John Wiley & Sons, 2006; (b) I. Ugi, Recent progress in the chemistry of multicomponent reactions, Pure Appl. Chem. 73(2001) 187-191; (c) V. Nair, C. Rajesh, A. Vinod, et al., Strategies for heterocyclic construction via novel multicomponent reactions based on isocyanides and nucleophilic carbenes, Acc. Chem. Res. 36(2003) 899-907; (d) D.J. Ramón, M. Yus, Asymmetric multicomponent reactions (AMCRs):the new frontier, Angew. Chem. Int. Ed. (2005) 1602-1634.
2. [2]
  (a) S. Benetti, R. Romagnoli, C. De Risi, G. Spalluto, V. Zanirato, Mastering b-keto esters, Chem. Rev. 95(1995) 1065-1114; (b) P. Langer, Regio-and diastereoselective cyclization reactions of free and masked 1,3-dicarbonyl dianions with 1,2-dielectrophiles, Chem. Eur. J. 7(2001) 3858-3866; (c) C. Simon, T. Constantieux, J. Rodriguez, Utilisation of 1,3-dicarbonyl derivatives in multicomponent reactions, Eur. J. Org. Chem. 2004(2004) 4957-4980.
3. [3]
  (a) B. Ganem, Strategies for innovation in multicomponent reaction design, Acc. Chem. Res. 42(2009) 463-472; (b) A. Dömling, Recent developments in isocyanide based multicomponent reactions in applied chemistry, Chem. Rev. 106(2006) 17-89.
4. [4]
  (a) G.L. Adams, P.J. Carroll, A.B. Smith III, Access to the akuammiline family of alkaloids:totalsynthesisof(+)-scholarisineA,J.Am.Chem.Soc.135(2012)519-528; (b) Y. Inaba, T. Hasuda, Y. Hitotsuyanagi, et al., Abietane diterpenoids and a sesquiterpene pyridine alkaloid from Euonymus lutchuensis, J. Nat. Prod. 76(2013) 1085-1090; (c) J.A. Bull, J.J. Mousseau, G. Pelletier, A.B. Charette, Synthesis of pyridine and dihydropyridine derivatives by regio-and stereoselective addition to N-activated pyridines, Chem. Rev. 112(2012) 2642-2713; (d) P.W. Ondachi, D.L. Comins, Synthesis of fused-ring nicotine derivatives from (S) nicotine, J. Org. Chem. 75(2010) 1706-1716; (e) A.D. Melhado, W.E. Brenzovich Jr., A.D. Lackner, F.D. Toste, Gold-catalyzed threecomponentcoupling:oxidative oxyarylation of alkenes, J. Am. Chem. Soc.132(2010) 8885-8887; (f) H.E. Montenegro, P. Ramírez-López, M.C. de la Torre, M. Asenjo, M.A. Sierra, Two versatile and parallel approaches to highly symmetrical open and closed natural product-based structures, Chem. Eur. J. 16(2010) 3798-3814; (g) S.A. Snyder, S.P. Breazzano, A.G. Ross, Y. Lin, A.L. Zografos, Total synthesis of diverse carbogenic complexity within the resveratrol class from a common building block, J. Am. Chem. Soc. 131(2009) 1753-1765.
5. [5]
  (a) K. Shekarrao, P.P. Kaishap, V. Saddanapu, et al., Microwave-assisted palladium mediated efficient synthesis of pyrazolo[3,4-b]pyridines, pyrazolo[3,4-b]quinolines, pyrazolo[1,5-a]pyrimidines and pyrazolo[1,5-a]quinazolines, RSC Adv. 4(2014) 24001-24006; (b) C. Kurumurthy, B. Veeraswamy, P.S. Rao, et al., Synthesis of novel 1,2,3-triazole tagged pyrazolo[3,4-b]pyridine derivatives and their cytotoxic activity, Bioorg. Med. Chem. Lett. 24(2014) 746-749; (c) D.K. Dodiya, A.R. Trivedi, V.B. Kataria, V.H. Shah, Advances in the synthesis of pyrazolo[3,4-b]pyridines, Curr. Org. Chem. 16(2012) 400-417; (d) M. El-Borai, H. Rizk, M. Abd-Aal, I. El-Deeb, Synthesis of pyrazolo[3,4-b]pyridines under microwave irradiation in multi-component reactions and their antitumor and antimicrobial activities-part 1, Eur. J. Med. Chem. 48(2012) 92-96; (e) Y. Hao, X.P. Xu, T. Chen, L.L. Zhao, S.J. Ji, Multicomponent approaches to 8-carboxylnaphthyl-functionalized pyrazolo[3,4-b]pyridinederivatives,Org.Biomol. Chem. 10(2012) 724-728; (f) D.B. Kendre, R.B. Toche, M.N. Jachak, Synthesis of pyrazolo[3,4-b]pyridines and attachment of amino acids and carbohydrate as linkers, J. Heterocycl. Chem. 45(2008) 1281-1286.
6. [6]
  (a) S. Wenglowsky, K.A. Ahrendt, A.J. Buckmelter, et al., Pyrazolopyridine inhibitors of B-Raf V600E. Part 2:structure-activity relationships, Bioorg. Med. Chem. Lett. 21(2011) 5533-5537; (b) J. Quiroga, J. Portilla, B. Insuasty, et al., Solvent-free microwave synthesis of bis-pyrazolo[3,4-b:4',3'-e]-pyridines and study of their antifungal properties, J. Heterocycl. Chem. 42(2005) 61-66; (c) R.N. Misra, D.B. Rawlins, H.Y. Xiao, et al., 1H-Pyrazolo[3,4-b]pyridine inhibitors of cyclin-dependent kinases, Bioorg. Med. Chem. Lett. 13(2003) 1133-1136; (d) A. Straub, J. Benet-Buckholz, R. Fröde, et al., Metabolites of orally active NOindependent pyrazolopyridine stimulators of soluble guanylate cyclase, Bioorg. Med. Chem. Lett. 10(2002) 1711-1717.
7. [7]
  E. De Clercq. Recent highlights in the development of new antiviral drugs[J]. Curr. Opin. Microbiol., 2005,8:552-560. doi: 10.1016/j.mib.2005.08.010
8. [8]
  R.G. Stein, J.H. Biel, T. Singh. Antimalarials. 4-Substituted 1H-pyrazolo[3,4-b]quinolines[J]. J. Med. Chem., 1970,13:153-155. doi: 10.1021/jm00295a049
9. [9]
  T. Sado, A. Inoue. Preparation of 1H-pyrazolo[3,4-b]pyrazines as blood platelet[J]. Chem. Abstr., 199078422k.
10. [10]
  H. de Mello, A. Echevarria, A.M. Bernardino, M. Canto-Cavalheiro, L.L. Leon. Antileishmanial pyrazolopyridine derivatives:synthesis and structure-activity relationship analysis[J]. J. Med. Chem., 2004,47:5427-5432. doi: 10.1021/jm0401006
11. [11]
  (a) S.A. Thompson, P.B. Wingrove, L. Connelly, P.J. Whiting, K.A. Wafford. Tracazolate reveals a novel type of allosteric interaction with recombinant γ-aminobutyric acid A receptors, Mol. Pharmacol., 2002,61: 861-869;(b) J.P. Stasch, E.M. Becker, C. Alonso-Alija, et al., NO-independent regulatory site on soluble guanylate cyclase, Nature, 2001,410: 212-215;(c) J. Zezula, A. Slany, W. Sieghart, Interaction of allosteric ligands with GABA A receptors containing one, two, or three different subunits[J]. Eur. J. Pharmacol., 1996,301:207-214. doi: 10.1016/0014-2999(96)00066-0
12. [12]
  (a) T. Fong, S. Heymsfield. Cannabinoid-1 receptor inverse agonists:current understanding of mechanism of action and unanswered questions, Int. J. Obes., 2009,33: 947-955;(b) C.S. Stika, G.A. Gross, G. Leguizamon, et al., A prospective randomized safety trial of celecoxib for treatment of preterm labor, Am. J. Obstet. Gynecol., 2002,187: 653-660;(c) K. Dilger, C. Herrlinger, J. Peters, et al., Effects of celecoxib and diclofenac on blood pressure, renal function, and vasoactive prostanoids in young and elderly subjects, J. Clin. Pharmacol., 2002,42: 985-994;(d) P. Chavatte, S. Yous, C. Marot, N. Baurin, D. Lesieur, Three-dimensional quantitative structure-activity relationships of cyclo-oxygenase-2(COX-2) inhibitors:a comparative molecular field analysis[J]. J. Med. Chem., 2001,44:3223-3230. doi: 10.1021/jm0101343
13. [13]
  J. Witherington, V. Bordas, A. Gaiba. 6-Aryl-pyrazolo[3,4-b]pyridines:potent inhibitors of glycogen synthase kinase-3(GSK-3)[J]. Bioorg. Med. Chem. Lett., 2003,13:3055-3057. doi: 10.1016/S0960-894X(03)00645-0
14. [14]
  A. Akahane, A. Tanaka, WO 2002100864 A1, 2003, Chem. Abstr. (2003) 24732a.
15. [15]
  K. Imaizumi, T. Sado, Jpn Kokai Tokkyo Koho JP 0680570[9480570] (Cl. A61K31/495) (22 Mar. 1994), Chem. Abstr. (1994) 91797w.
16. [16]
  S.A. Saggar, J.T. Sisko, T.J. Tucker. HIV reverse transcriptase inhibitors[J]. Google Patents, 2010.
17. [17]
  G. Chiu, S. Li, P. Connolly. 3-(Benzimidazolyl)-pyrazolopyridines as protein kinase inhibitors, their preparation, pharmaceutical compositions, and use in therapy[J]. PCT Int. Appl. WO, 20062006130673.
18. [18]
  S. Huang, R. Lin, Y. Yu. Synthesis of 3-(1H-benzimidazol-2-yl)-5-isoquinolin-4-ylpyrazolo[1,2-b]pyridine, a potent cyclin dependent kinase 1(CDK1) inhibitor[J]. Bioorg. Med. Chem. Lett., 2007,17:1243-1245. doi: 10.1016/j.bmcl.2006.12.031
19. [19]
  D.B. Kendre, R.B. Toche, M.N. Jachak. Synthesis of novel dipyrazolo[3,4-b:3,4-d]pyridines and study of their fluorescence behavior[J]. Tetrahedron, 2007,63:11000-11004. doi: 10.1016/j.tet.2007.08.052
20. [20]
  M.A. El Mhammedi, A. Chtaini. Investigation of the inhibitive effect of pyrazolo[3,4-b]pyridine on corrosion of stainless steel in 1 M HCl solutions[J]. Leonardo Electron. J. Pract. Technol., 2007:37-46.
21. [21]
  (a) K. Balamurugan, S. Perumal, J.C. Menéndez, New four-component reactions in water:a convergent approach to the metal-free synthesis of spiro[indoline/acenaphthylene-3,4'-pyrazolo[3,4-b]pyridine derivatives, Tetrahedron 67(2011) 3201-3208; (b) A. Soliman, Synthesis of novel pyrazolopyridine and pyridopyrimidine derivatives, J. Heterocycl. Chem. 48(2011) 592-596; (c) A. Rahmati, Synthesis of 4-aryl-3-methyl-6-oxo-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine-5-carbonitrile via a one-pot, three-component reaction, Tetrahedron Lett. 51(2010) 2967-2970; (d) A. Díaz-Ortiz, J.R. Carrillo, F.P. Cossío, et al., Synthesis of pyrazolo[3,4-b]pyridines by cycloaddition reactions under microwave irradiation, Tetrahedron 56(2000) 1569-1577.
22. [22]
  (a) C.S. Hege, S.M. Schiller, Non-toxic catalysts for ring-opening polymerizations of biodegradable polymers at room temperature for biohybrid materials, Green Chem. 16(2014) 1410-1416; (b) P.K. Sahu, P.K. Sahu, S.K. Gupta, D.D. Agarwal, Chitosan:an efficient, reusable, and biodegradable catalyst for green synthesis of heterocycles, Ind. Eng. Chem. Res. 53(2014) 2085-2091; (c) I. Siddiqui, P. Rai, A. Srivastava, Chitosan:an efficient promoter for the synthesis of 2-aminopyrimidine-5-carbonitrile derivatives in solvent free conditions, New J. Chem. 38(2014) 3791-3795; (d) E. Mosaddegh, A. Hassankhani, Application and characterization of eggshell as a new biodegradable and heterogeneous catalyst in green synthesis of 7,8-dihydro-4H-chromen-5(6H)-ones, Catal. Commun. 33(2013) 70-75; (e) Z.N. Siddiqui, K. Khan, Friedlander synthesis of novel benzopyranopyridines in the presence of chitosan as heterogeneous, efficient and biodegradable catalyst under solvent-free conditions, New J. Chem. 37(2013) 1595-1602; (f) G.Y. Sun, J.T. Hou, J.J. Dou, et al., Xanthan sulfuric acid as an efficient biodegradable and recyclable catalyst for the one-pot synthesis of α-amino phosphonates, J. Chin. Chem. Soc. 57(2010) 1315-1320.
23. [23]
  (a) R.Y. Guo, Z.M. An, L.P. Mo, et al., Meglumine:a novel and efficient catalyst for one-pot, three-component combinatorial synthesis of functionalized 2-amino-4H-pyrans, ACS Comb. Sci. 15(2013) 557-563; (b) J. Yang, H. Li, M. Li, J. Peng, Y. Gu, Multicomponent reactions of β-ketosulfones and formaldehyde in a bio-based binary mixture solvent system composed of meglumine and gluconic acid aqueous solution, Adv. Synth. Catal. 354(2012) 688-700.
24. [24]
  (a) S. Tabassum, S. Govindaraju, R.R. Khan, M.A. Pasha, Ultrasound mediated, iodine catalyzed green synthesis of novel 2-amino-3-cyano-4H-pyran derivatives, Ultrason. Sonochem. 24(2015) 1-7; (b) S. Tabassum, S. Govindaraju, R.R. Khan, M.A. Pasha, Ultrasound mediated, green innovation for the synthesis of polysubstituted 1,4-dihydropyridines, RSC Adv. 6(2016) 29802-29810; (c) K.B. Ramesh, M.A. Pasha, Study on one-pot four-component synthesis of 9-aryl-hexahydro-acridine-1,8-diones using SiO₂-I as a new heterogeneous catalyst and their anticancer activity, Bioorg. Med. Chem. Lett. 24(2014) 3907-3913; (d) S.H.S.Azzam,A.Siddekha,M.A.Pasha,One-potfour-componentsynthesisof some novel octahydroquinolindiones using ZnO as an efficient catalyst in water, Tetrahedron Lett. 53(2012) 6306-6309.
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