Citation: Zhou Chen-Feng, Li Jian-Jun, Su Wei-Ke. Morpholine triflate promoted one-pot, four-component synthesis of dihydropyrano[2, 3-c] pyrazoles[J]. Chinese Chemical Letters, ;2016, 27(11): 1686-1690. doi: 10.1016/j.cclet.2016.05.010 shu

Morpholine triflate promoted one-pot, four-component synthesis of dihydropyrano[2, 3-c] pyrazoles

  • Corresponding author: Li Jian-Jun, lijianjun@zjut.edu.cn Su Wei-Ke, pharmlab@zjut.edu.cn
  • Received Date: 9 March 2016
    Revised Date: 4 May 2016
    Accepted Date: 10 May 2016
    Available Online: 25 November 2016

Figures(3)

  • A one-pot, four-component reaction of ethyl acetoacetate, hydrazine hydrate, aldehydes, and malononitrile was discussed using Lewis acid catalyst morpholine triflate (MorT) to afford a series of dihydropyrano[2, 3-c] pyrazoles, which were generally catalyzed by organic alkalis.Moderate to excellent yields, no chromatographic purification, and evasion of environmentally hazardous solvents in the reaction process make this protocol very useful for academia and industry.
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    1. [1]

      (a) C. Allais, J.M. Grassot, J. Rodriguez, T. Constantieux, Metal-free multicomponent syntheses of pyridines, Chem. Rev. 114(2014) 10829-10868;
      (b) K. Tanaka, F. Toda, Solvent-free organic synthesis, Chem. Rev. 100(2000) 1025-1074;
      (c) A. Roucoux, J. Schulz, H. Patin, Reduced transition metal colloids: a novel family of reusable catalysts, Chem. Rev. 102(2002) 3757-3778.

    2. [2]

      (a) L.A. Thompson, Recent applications of polymer-supported reagents and scavengers in combinatorial, parallel, or multistep synthesis, Curr. Opin. Chem. Biol. 4(2000) 324-337;
      (b) A. Nefzi, J.M. Ostresh, R.A. Houghten, The current status of heterocyclic combinatorial libraries, Chem. Rev. 97(1997) 449-472.

    3. [3]

      Prajapati S.P., Patel D.P., Patel P.S.. Synthesis, characterization and antimicrobial activity of 6-amino-4-(substitutedphenyl)-1-(2, 4-dinitrophenyl)-3-methyl-1, 4-dihydropyrano[2, 3-c]pyrazole-5-carbonitrile derivatives[J]. J Chem. Pharm. Res., 2012,4:2652-2655.

    4. [4]

      Chaudhari S.A., Patil S.R., Patil V.M.. Synthesis of pyrano[2, 3-d]pyridine, pyrazolo[3, 4-b]pyridine derivatives by microwave irradiation and study of their insecticidal activity[J]. J. Chem. Pharm. Res., 2015,7:476-482.

    5. [5]

      Zaki M.E.A., Soliman H.A., Hiekal O.A., Rashad A.E.. Pyrazolopyranopyrimidines as a class of anti-inflammatory agents[J]. Z. Naturforsch. C, 2006,61:1-5.  

    6. [6]

      (a) F.M. Abdelrazek, P. Metz, N.H. Metwally, et al., Synthesis and molluscicidal activity of new cinnoline and pyrano[2, 3-c] pyrazole derivatives, Arch. Pharm. Chem. Life Sci. 339(2006) 456-460;
      (b) F.M. Abdelrazek, P. Metz, O. Kataeva, et al., Synthesis and molluscicidal activity of new chromene and pyrano[2, 3-c]pyrazole derivatives, Arch. Pharm. Chem. Life Sci. 340(2007) 543-548.

    7. [7]

      (a) N. Foloppe, L.M. Fisher, R. Howes, et al., Identification of chemically diverse Chk1 inhibitors by receptor-based virtual screening, Bioorg. Med. Chem. 14(2006) 4792-4802;
      (b) A. Kimata, H. Nakagawa, R. Ohyama, T. Fukuuchi, et al., New series of antiprion compounds: pyrazolone derivatives have the potent activity of inhibiting protease-resistant prion protein accumulation, J. Med. Chem. 50(2007) 5053-5056.

    8. [8]

      (a) A.M.G. James, J.S. Peter, Heterocyclic tautomerism, part 12. The structure of the product of reaction between 3-methyl-1-phenyl-2-pyrazolin-5-one and tetracyanoethylene, Arkivoc 2(2001) 32-36;
      (b) L.A.Rodinovskaya, A.V.Gromova, A.M.Shestopalov, etal., Synthesisof6-amino-4-aryl-5-cyano-3-(3-cyanopyridin-2-ylthiomethyl)-2, 4-dihydropyrano[2, 3-c]pyrazoles and their hydrogenated analogs. Molecular structure of 6-amino-5-cyano-3-(3-cyano-4, 6-dimethylpyridin 2-ylthiomethyl)-4-(2-nitrophenyl)-2, 4-dihydropyrano[2, 3-c]pyrazole, Russ, Chem. Bull. Int. Ed. 52(2003) 2207-2213.

    9. [9]

      Peng Y.Q., Song G.H., Dou R.L.. Surface cleaning under combined microwave and ultrasound irradiation: flash synthesis of 4H-pyrano[2, 3-c] pyrazoles in aqueous media[J]. Green Chem., 2006,8:573-575. doi: 10.1039/b601209d

    10. [10]

      (a) A.M. Shestopalov, Y.M. Emeliyanova, A.A. Shestopalov, et al., Cross-condensation of derivatives of cyanoacetic acid and carbonyl compounds. Part 1: singlestage synthesis of 1’-substituted 6-amino-spiro-4-(piperidine-4)-2H, 4H-pyrano[2, 3-c]pyrazole-5-carbonitriles, Tetrahedron 59(2003) 7491-7496;
      (b) A.M. Shestopalov, Y.M. Emeliyanova, A.A. Shestopalov, et al., One-step synthesis of substituted 6-amino-5-cyanospiro-4-(piperidine-40)-2H, 4H-dihydropyrazolo[3, 4-b]pyrans, Org. Lett. 4(2002) 423-425.

    11. [11]

      (a) Y.M. Litvinov, A.A. Shestopalov, L.A. Rodinovskaya, et al., New convenient four-component synthesis of 6-amino-2, 4-dihydropyrano[2, 3-c]pyrazol-5-carbonitriles and one-pot synthesis of 60-aminospiro[(3H)-indol-3, 40-pyrano[2, 3-c]pyrazol]-(1H)-2-on-50-carbonitriles, J. Comb. Chem. 11(2009) 914-919;
      (b) G. Vasuki, K. Kumaravel, Rapid four-component reactions in water: synthesis of pyranopyrazoles, Tetrahedron Lett. 49(2008) 5636-5638;
      (c) J.M. Khurana, B. Nand, S. Kumar, Rapid synthesis of polyfunctionalized pyrano[2, 3-c]pyrazoles via multicomponent condensation in room-temperature ionic liquids, Synth. Commun. 41(2011) 405-410;
      (d) H. Mecadon, M.R. Rohman, I. Kharbangar, et al., L-Proline as an efficicent 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;
      (e) K. Kanagaraj, K. Pitchumani, Solvent-free multicomponent synthesis of pyranopyrazoles: per-6-amino-b-cyclodextrin as a remarkable catalyst and host, Tetrahedron Lett. 51(2010) 3312-3316;
      (f) K. Ablajan, L.J. Wang, A. Tuoheti, et al., An efficient four-component, one-pot synthesis of 6-amino-4-aryl-3-methyl-2, 4-dihydropyrano[2, 3-c] pyrazole-5-carbonitriles under phasetransfer catalyst, Lett. Org. Chem. 9(2012) 639-643;
      (g) J.M. Khurana, A. Chaudhary, Efficient and green synthesis of 4H-pyrans and 4H-pyrano[2, 3-c] pyrazoles catalyzed by task-specific ionic liquid[bmim]OH under solvent-free conditions, Green Chem. Lett. Rev. 5(2012) 633-638;
      (h) X.J. Li, H.Y. Guo, One-pot synthesis of 1, 4-dihydropyrano[2, 3-c] pyrazoies cataiyzed by basic ionic liquids, Chin. J. Org. Chem. 32(2012) 127-132;
      (i) A.R. Moosavi-Zare, M.A. Zolfigol, E. Noroozizadeh, et al., Synthesis of 6-amino-4-(4-methoxyphenyl)-5-cyano-3-methyl-1-phenyl-1, 4-dihydropyrano[2, 3-c]pyrazoles using disulfonic acid imidazolium chloroaluminate as a dual and heterogeneous catalyst, New J. Chem. 37(2013) 4089-4094;
      (j) R.Y. Guo, Z.M. An, L.P. Mo, et al., Meglumine promoted one-pot, four-component synthesis of pyranopyrazole derivatives, Tetrahedron 69(2013) 9931-9938;
      (k) M.Bihani, P.P. Bora, G.Bez, etal., AmberlystA21catalyzedchromatographyfree method for multicomponent synthesis of dihydropyrano[2, 3-c]pyrazoles in ethanol, ACS Sustain. Chem. Eng. 1(2013) 440-447;
      (l) H. Mecadon, M.R. Rohman, M. Rajbangshi, et al., g-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;
      (m) S. Paul, K. Pradhan, S. Ghosh, et al., Uncapped SnO2 quantum dot catalyzed cascade assembling of four components: a rapid and green approach to the pyrano[2, 3-c]pyrazole andspiro-2-oxindole derivatives, Tetrahedron 70(2014) 6088-6099;
      (n) R.S. Balaskar, S.N. Gavade, M.S. Mane, et al., Greener approach towards the facile synthesis of 1, 4-dihydropyrano[2, 3-c]pyrazol-5-yl cyanide derivatives at room temperature, Chin. Chem. Lett. 21(2010) 1175-1179;
      (o) N. Iravani, M. Keshavarz, H.A.S. Kish, et al., Tin sulfide nanoparticles supported on activated carbon as an efficient and reusable Lewis acid catalyst for three-component one-pot synthesis of 4H-pyrano[2, 3-c]pyrazole derivatives, Chin. J. Catal. 36(2015) 626-633.

    12. [12]

      (a) J.J. Li, L.M. Lu, W.K. Su, A new strategy for the synthesis of benzoxanthenes catalyzed by proline triflate in water, Tetrahedron Lett. 51(2010) 2434-2437;
      (b) J.J. Li, P. He, C.M. Yu, DPTA-catalyzed one-pot regioselective synthesis of polysubstituted pyridines and 1, 4-dihydropyridines, Tetrahedron 68(2012) 4138-4144;
      (c) J.J. Li, J. Sun, W.K. Su, Diphenylammonium triflate: a novel and efficient catalyst for synthesis of spiro-heterocyclic compounds, Lett. Org. Chem. 7(2010) 314-318;
      (d) X.J. Shi, J. Li, W.H. Zhong, et al., Synthesis of 1 H-indazolo[2, 1-b] phthalazinetriones catalysed by proline triflate under solvent-free conditions, J. Chem. Res. 36(2012) 17-20;
      (e) F. Malamiri, S. Khaksar, Pentafluorophenylammonium triflate (PFPAT): a new organocatalyst for the one-pot three-component synthesis of a-aminophosphonates, J. Chem. Sci. 126(2014) 807-811;
      (f) B. Karimi, M. Ghoreishi-Nezhad, Highly chemoselective acetalization of carbonyl compounds catalyzed by a novel recyclable ammonium triflate-functionalized silica, J. Mol. Catal. A: Chem. 277(2007) 262-265;
      (g) A. Del Zotto, W. Baratta, A. Felluga, et al., Addition of secondary amines to activated alkenes promoted by Pd(Ⅱ) complexes: use of ammonium salts as cocatalysts, Inorg. Chim. Acta 358(2005) 2749-2754.

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