Citation: Ying Li, Chun-E. Dong. Effi cient synthesis of fused pyrazoles via simple cyclization of o-alkynylchalcones with hydrazine[J]. Chinese Chemical Letters, ;2015, 26(5): 623-626. doi: 10.1016/j.cclet.2015.01.002 shu

Effi cient synthesis of fused pyrazoles via simple cyclization of o-alkynylchalcones with hydrazine

Ying Li ,
Chun-E. Dong ^,

1.
Key Laboratory of Combinatorial Biosynthesis and Drug Discovery, Wuhan University, Ministry of Education, Wuhan University School of Pharmaceutical Sciences, Wuhan 430071, China

Corresponding author: Chun-E. Dong,
Received Date: 13 November 2014
Available Online: 4 January 2015
Fund Project: We are grateful to the Fundamental Research Funds for the Central Universities (No. 2042014kf0248) for support of this research. (No. 2042014kf0248)

The synthesis of pyrazole derivatives from o-alkynylchalcones and hydrazine via simple cyclization is described. This greener syntheticmethodology provides a straightforward approach to the synthesis of a variety of pyrazole derivatives under mild reaction condition.
- Pyrazole,
- o-Alkynylchalcones,
- Hydrazine,
- Cyclization
1. [1]
  [1] A.R. Katritzky, C.W. Rees, K.T. Potts, Comprehensive Heterocyclic Chemistry: The Structure, Reactions, Synthesis and Uses of Heterocyclic Compounds, Pergamon Press, Oxford, UK, 1984.
2. [2]
  [2] (a) J. Reedijk, Pyrazoles and imidazoles as ligands: Part I. Some simple metal (II) perchlorates and tetrafluoroborates solvated by neutral pyrazole and imidazole, Recl. Trav. Chim. Pays-Bas 88 (1969) 1451-1470;
3. [3]
  (b) J. Catalan, F. Fabero, R.M. Claramunt, et al., New ultraviolet stabilizers: 3- and 5-(2'-hydroxyphenyl)pyrazoles, J. Am. Chem. Soc. 114 (1992) 5039-5048.
4. [4]
  [3] G. Pinna, G. Loriga, P. Lazzari, et al., Tricyclic pyrazoles, Part 6. Benzofuro[3,2- c]pyrazole: a versatile architecture for CB2 selective ligands, Eur. J. Med. Chem. 82 (2014) 281-292.
5. [5]
  [4] K.O. Mohammed, Y.M. Nissan, Synthesis, molecular docking, and biological evaluation of some novel hydrazones and pyrazole derivatives as anti-inflammatory agents, Chem. Biol. Drug Des. 84 (2014) 473-488.
6. [6]
  [5] H.X. Dai, A.F. Stepan, M.S. Plummer, Y.H. Zhang, J.Q. Yu, Divergent C-H functionalizations directed by sulfonamide pharmacophores: late-stage diversification as a tool for drug discovery, J. Am. Chem. Soc. 133 (2011) 7222-7228.
7. [7]
  [6] (a) Z. Ozdemir, H.B. Kandilci, B. Gumusel, U. Calis, A.A. Bilgin, Synthesis and studies on antidepressant and anticonvulsant activities of some 3-(2-furyl)- pyrazoline derivatives, Eur. J. Med. Chem. 42 (2007) 373-379;
8. [8]
  (b) S.T. Heller, S.R. Natarajan, 1,3-Diketones from acid chlorides and ketones: a rapid and general one-pot synthesis of pyrazoles, Org. Lett. 8 (2006) 2675-2678;
9. [9]
  (c) B.A. Bhat, K.L. Dhar, S.C. Puri, et al., Synthesis and biological evaluation of chalcones and their derived pyrazoles as potential cytotoxic agents, Bioorg. Med. Chem. Lett. 15 (2005) 3177-3180.
10. [10]
  [7] (a) Y. Wang, L. Liu, L. Zhang, Combining Zn ion catalysis with homogeneous gold catalysis: an efficient annulation approach to N-protected indoles, Chem. Sci. 4 (2013) 739-746;
11. [11]
  (b) S. Cacchi, G. Fabrizi, Synthesis and functionalization of indoles through palladium-catalyzed reactions, Chem. Rev. 105 (2005) 2873-2920.
12. [12]
  [8] (a) Y.F. Wang, K.K. Toh, J.Y. Lee, S. Chiba, Synthesis of isoquinolines from α-aryl vinyl azides and internal alkynes by Rh-Cu bimetallic cooperation, Angew. Chem. Int. Ed. 50 (2011) 5927-5931;
13. [13]
  (b) P.C. Too, Y.F. Wang, S. Chiba, Rhodium(III)-catalyzed synthesis of isoquinolines from aryl ketone o-acyloxime derivatives and internal alkynes, Org. Lett. 12 (2010) 5688-5691;
14. [14]
  (c) Q. Huang, J.A. Hunter, R.C. Larock, Synthesis of substituted isoquinolines by electrophilic cyclization of iminoalkynes, J. Org. Chem. 67 (2002) 3437-3444.
15. [15]
  [9] (a) L. Zhou, Y. Shi, Q. Xiao, et al., CuBr-catalyzed coupling of N-tosylhydrazones and terminal alkynes: synthesis of benzofurans and indoles, Org. Lett. 13 (2011) 968-971;
16. [16]
  (b) I. Nakamura, Y. Mizushima, Y. Yamamoto, Synthesis of 2,3-disubstituted benzofurans by platinum-olefin-catalyzed carboalkoxylation of o-alkynylphenyl acetals, J. Am. Chem. Soc. 127 (2005) 15022-15023.
17. [17]
  [10] (a) T. Yao, R.C. Larock, Synthesis of isocoumarins and α-pyrones via electrophilic cyclization, J. Org. Chem. 68 (2003) 5936-5942;
18. [18]
  (b) R.K. Chinnagolla, M. Jeganmohan, Regioselective synthesis of isocoumarins by ruthenium-catalyzed aerobic oxidative cyclization, Chem. Commun. 48 (2012) 2030-2032.
19. [19]
  [11] X. Xu, P.Y. Zavalij, W. Hu, M.P. Doyle, Vinylogous reactivity of enol diazoacetates with donor-acceptor substituted hydrazones, synthesis of substituted pyrazole derivatives, J. Org. Chem. 78 (2013) 1583-1588.
20. [20]
  [12] X. Pan, Y. Luo, J. Wu, Route to pyrazolo[5,1-a]isoquinolines via a copper-catalyzed tandem reaction of 2-alkynylbromobenzene with pyrazole, J. Org. Chem. 78 (2013) 5756-5760.
21. [21]
  [13] B. Chen, C.Zhu,Y.Tang, S.Ma,Copper-mediatedpyrazole synthesis from2,3-allenoates or 2-alkynoates, amines and nitriles, Chem. Commun. 50 (2014) 7677-7679.
22. [22]
  [14] X. Zhang, J. Kang, P. Niu, et al., I2-mediated oxidative C-N bond formation for metal-free one-pot synthesis di,tri, and tetrasubstituted pyrazoles from α,ß unsaturated aldehydes/ketones and hydrazines, J. Org. Chem. 79 (2014) 10170-10178.
23. [23]
  [15] R.R. Merchant, D.M. Allwood, D.C. Blakemore, S.V. Ley, Regioselective preparation of saturated spirocyclic and ring-expanded fused pyrazoles, J. Org. Chem. 79 (2014) 8800-8811.
24. [24]
  [16] (a) C. Dong, L. Xie, X. Mou, Y. Zhong, W. Su, Facile synthesis of 1,3,4-benzotriazepines and 1-arylamide-1H-indazoles via palladium-catalyzed cyclization of aryl isocyanates and aryl hydrazones under microwave irradiation, Org. Biomol. Chem. 8 (2010) 4827-4830;
25. [25]
  (b) C. Dong, Z. Liao, X. Xu, H. Zhou, A new pathway for phthalazine derivatives via metal-free cyclization of ortho-alkynylphenyl ketones and hydrazine, J. Heterocycl. Chem. 51 (2014) 1282-1286.
26. [26]
  [17] J. Qiao, B. Liu, Z. Liao, One-pot to fused pyrazoles by a double cyclization of oalkynylaldehydes with ketones and hydrazine under metal-free condition, Tetrahedron 70 (2014) 3782-3787.
27. [27]
  [18] S.K. Pawar, C.D. Wang, S. Bhunia, A.M. Jadhav, R.S. Liu, Gold-catalyzed formal cycloaddition of 2-ethynylbenzyl ethers with organic oxides and α-diazoesters, Angew. Chem. Int. Ed. 52 (2013) 7559-7563.
28. [28]
  [19] X. Li, L. Li, Y. Tang, et al., Chemoselective conjugate reduction of α,β-unsaturated ketones catalyzed by rhodium amido complexes in aqueous media, J. Org. Chem. 75 (2010) 2981-2988.
29. [29]
  [20] A. Martínez, M. Fernández, J.C. Estévez, R.J. Estévez, L. Castedo, Studies on the chemistry of 2-(2-oxo-3-phenylpropyl)-benzaldehydes: novel total synthesis of 3-phenylnaphthalen-2-ols and 2-hydroxy-3-phenyl-1,4-naphthoquinones, Tetrahedron 61 (2005) 485-492.
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