Citation: Yogesh B. Wagh, Yogesh A. Tayade, Swapnil A. Padvi, Bhupesh S. Patil, Nilesh B. Patil, Dipak S. Dalal. A cesium fluoride promoted efficient and rapid multicomponent synthesis of functionalized 2-amino-3-cyano-4H-pyran and spirooxindole derivatives[J]. Chinese Chemical Letters, ;2015, 26(10): 1273-1277. doi: 10.1016/j.cclet.2015.06.014 shu

A cesium fluoride promoted efficient and rapid multicomponent synthesis of functionalized 2-amino-3-cyano-4H-pyran and spirooxindole derivatives

1.
School of Chemical Sciences, North Maharashtra University, Jalgaon 425 001, MS, India

Corresponding author: Dipak S. Dalal,
Received Date: 13 March 2015
Available Online: 18 May 2015
Fund Project: One of the authors (Y.B.W.) acknowledges UGC, New Delhi for SAP fellowship under the scheme 'Research Fellowship in Sciences for Meritorious Students'. The authors are also grateful to SAIF Panjab University for providing analytical facilities for characterization of compounds. (Y.B.W.)

A rapid, one-pot and highly efficient protocol for the synthesis of pharmaceutically interesting functionalized 2-amino-3-cyano-4H-pyran and spirooxindole derivatives has been developed using commercially available CsF as a catalyst in the reaction of malononitrile and aryl aldehydes or isatins with 1, 3-cyclohexanediones. The major advantages of this methodology are excellent yield at ambient temperature, very short reaction time (5-10 min), and use of an inexpensive catalyst.
- Cesium fluoride,
- 2-Amino-3-cyano-4H-pyrans,
- Spirooxindoles,
- Rapid synthesis,
- Multicomponent reactions
1. [1]
  [1] B. Sharifzadeh, N.O. Mahmoodi, M. Mamaghani, et al., Facile regioselective synthesis of novel bioactive thiazolyl-pyrazoline derivatives via a three-component reaction and their antimicrobial activity, Bioorg. Med. Chem. Lett. 23(2013) 548-551.
2. [2]
  [2] R. Hosseinnia, M. Mamaghani, K. Tabatabaeian, F. Shirini, M. Rassa, An expeditious regioselective synthesis of novel bioactive indole-substituted chromene derivatives via one-pot three-component reaction, Bioorg. Med. Chem. Lett. 22(2012) 5956-5960.
3. [3]
  [3] N. Foroughifar, S. Ebrahimi, One-pot synthesis of 1,3-thiazolidin-4-one using bi(SCH₂COOH)₃ as catalyst, Chin. Chem. Lett. 24(2013) 389-391.
4. [4]
  [4] R. Baharfar, S.M. Baghbanian, Synthesis of novel uracil based 2,5-diaminofurans using multi-component reactions, Chin. Chem. Lett. 23(2012) 677-680.
5. [5]
  [5] L. Bonsignore, G. Loy, D. Secci, A. Calignano, Synthesis and pharmacological activity of 2-oxo-(2H) 1-benzopyran-3-carboxamide derivatives, Eur. J. Med. Chem. 28(1993) 517-520.
6. [6]
  [6] L.F. Tietze, Secologanin, a biogenetic key compound-synthesis and biogenesis of the iridoid and secoiridoid glycosides, Angew. Chem. Int. Ed. Engl. 22(1983) 828-841.
7. [7]
  [7] E.A.A. Hafez, M.H. Elnagdi, A.G.A. Elagamey, et al., Nitriles in heterocyclic synthesis:novel synthesis of benzo[c]coumarin and of benzo[c]pyrano[3,2-c]quinoline derivatives, Heterocycles 26(1987) 903-907.
8. [8]
  [8] (a) H. Hong, L.J. Huang, D.W. Teng, A spirocyclic oxindole analogue:synthesis and antitumor activities, Chin. Chem. Lett. 22(2011) 1009-1012;
9. [9]
  (b) D.-C. Wang, Y.-M. Xie, C. Fan, et al., Efficient and mild cyclization procedures for the synthesis of novel 2-amino-4H-pyran derivatives with potential antitumor activity, Chin. Chem. Lett. 25(2014) 1011-1013.
10. [10]
  [9] D. Kumar, V.B. Reddy, S. Sharad, et al., A facile one-pot green synthesis and antibacterial activity of 2-amino-4H-pyrans and 2-amino-5-oxo-5,6,7,8-tetrahydro-4H-chromenes, Eur. J. Med. Chem. 44(2009) 3805-3809.
11. [11]
  [10] C.B. Sangani, D.C. Mungra, M.P. Patel, et al., Synthesis and in vitro antimicrobial screening of new pyrano[4,3-b]pyran derivatives of 1H-pyrazole, Chin. Chem. Lett. 23(2012) 57-60.
12. [12]
  [11] (a) W. Kemnitzer, S. Kasibhatla, S. Jiang, et al., Discovery of 4-aryl-4H-chromenes as a new series of apoptosis inducers using a cell- and caspase-based highthroughput screening assay. 2. Structure-activity relationships of the 7- and 5-, 6-, 8-positions, Bioorg. Med. Chem. Lett. 15(2005) 4745-4751;
13. [13]
  (b) S. Kasibhatla, H. Gourdeau, K. Meerovitch, et al., Discovery and mechanism of action of a novel series of apoptosis inducers with potential vascular targeting activity, Mol. Cancer Ther. 3(2004) 1365-1374.
14. [14]
  [12] D. Armesto, W.M. Horspool, N. Martin, et al., Synthesis of cyclobutenes by the novel photochemical ring contraction of 4-substituted 2-amino-3,5-dicyano-6-phenyl-4H-pyrans, J. Org. Chem. 54(1989) 3069-3072.
15. [15]
  [13] M. Chennapuram, N.R. Emmadi, C. Bingi, et al., Group-assisted purification (GAP) chemistry for dihydrofurans:water as a medium for catalyst free synthesis in a one pot four component reaction, Green Chem. 16(2014) 3237-3246.
16. [16]
  [14] A.R. Moosavi-Zare, M.A. Zolfigol, O. Khaledian, et al., Tandem Knoevenagel- Michael-cyclocondensation reactions of malononitrile, various aldehydes and dimedone using acetic acid functionalized ionic liquid, New J. Chem. 38(2014) 2342-2347.
17. [17]
  [15] M.G. Dekamin, M. Eslami, Highly efficient organocatalytic synthesis of diverse and densely functionalized 2-amino-3-cyano-4H-pyrans under mechanochemical ball milling, Green Chem. 16(2014) 4914-4921.
18. [18]
  [16] M.N. Elinson, A.S. Dorofeev, S.K. Feducovich, et al., The implication of electrocatalysis in MCR strategy:electrocatalytic multicomponent transformation of cyclic 1,3-diketones, aldehydes and malononitrile into substituted 5,6,7,8-tetrahydro-4H-chromenes, Eur. J. Org. Chem. 19(2006) 4335-4339.
19. [19]
  [17] V.M. Joshi, L.P.B. Rupali, Throat, et al., Novel one-pot synthesis of 4H-chromene derivatives using amino functionalized silica gel catalyst, Chin. Chem. Lett. 25(2014) 455-458.
20. [20]
  [18] (a) N. Azizi, S. Dezfooli, M.M. Hashemi, Synthesis of spirooxindole in deep eutectic solvent, J. Mol. Liq. 194(2014) 62-67;
21. [21]
  (b) Y. Li, H. Chen, C. Shi, et al., Efficient one-pot synthesis of spirooxindole derivatives catalyzed by L-proline in aqueous medium, J. Comb. Chem. 12(2010) 231-237;
22. [22]
  (c) M. Kidwai, A. Jahan, N.K. Mishra, et al., Gold(III) chloride (HAuCl₄·3H₂O) in PEG:a new and efficient catalytic system for the synthesis of functionalized spirochromenes, Appl. Catal. A 425(2012) 35-43;
23. [23]
  (d) B.M. Rao, G.N. Reddy, T.V. Reddy, et al., Carbon-SO₃H:a novel and recyclable solid acid catalyst for the synthesis of spiro[4H-pyran-3,30-oxindoles], Tetrahedron Lett. 54(2013) 2466-2471.
24. [24]
  [19] X. Lian, Y. Huang, Y. Li, et al., A green synthesis of tetrahydrobenzo[b]pyran derivatives through three-component condensation using N-methylimidazole as organocatalyst, Monatsh. Chem. 139(2008) 129-131.
25. [25]
  [20] T.S. Jin, A.Q. Wang, F. Shi, et al., Hexadecyldimethyl benzyl ammonium bromide:an efficient catalyst for a clean one-pot synthesis of tetrahydrobenzopyran derivatives in water, ARKIVOC xiv (2006) 78-86.
26. [26]
  [21] R. Hekmatshoar, S. Majedi, K. Bakhtiari, Sodium selenate catalyzed simple and efficient synthesis of tetrahydro benzo[b]pyran derivatives, Catal. Commun. 9(2008) 307-310.
27. [27]
  [22] D. Tahmassebi, J. Bryson, S. Binz, 1,4-Diazabicyclo[2.2.2] octane as an efficient catalyst for a clean, one-pot synthesis of tetrahydrobenzo[b]pyran derivatives via multicomponent reactioninaqueousmedia, Synth.Commun.41(2011)2701-2711.
28. [28]
  [23] X. Wang, D. Shi, S. Tu, et al., Convenient synthesis of 5-oxo-5,6,7,8-tetrahydro-4Hbenzo-[b]-pyran derivatives catalyzed by KF-alumina, Synth. Commun. 33(2003) 119-126.
29. [29]
  [24] G. Sabitha, K. Arundhathi, K. Sudhakar, et al., Cerium(III) chloride-catalyzed onepot synthesis of tetrahydrobenzo[b]pyrans, Synth. Commun. 39(2009) 433-442.
30. [30]
  [25] S. Balalaie, M. Sheikh-Ahmadi, M. Bararjanian, Tetra-methyl ammonium hydroxide:an efficient and versatile catalyst for the one-pot synthesis of tetrahydrobenzo[b]pyran derivatives in aqueous media, Catal. Commun. 8(2007) 1724-1728.
31. [31]
  [26] S. Balalaie, M. Bararjanian, M. Sheikh-Ahmadi, et al., Diammonium hydrogen phosphate:an efficient and versatile catalyst for the one pot synthesis of tetrahydrobenzo[b]pyran derivatives in aqueous media, Synth. Commun. 37(2007) 1097-1108.
32. [32]
  [27] M.M. Heravi, Y.S. Beheshtiha, Z. Pirnia, et al., One-pot, three-component synthesis of 4H-pyrans using Cu(II) oxymetasilicate, Synth. Commun. 39(2009) 3663-3667.
33. [33]
  [28] M. Seifi, H. Sheibani, High surface area MgO as a highly effective heterogeneous base catalyst for three-component synthesis of tetrahydrobenzopyran and 3,4-dihydropyrano[c]chromene derivatives in aqueous media, Catal. Lett. 126(2008) 275-279.
34. [34]
  [29] R.S. Bhosale, C.V. Magar, K.S. Solanke, et al., Molecular iodine:an efficient catalyst for the synthesis of tetrahydrobenzo[b]pyrans, Synth. Commun. 37(2007) 4353-4357.
35. [35]
  [30] G.K. Friestad, B.P. Branchaud, W. Navarrini, M. Sansotera, Cesium fluoride, in:e-EROSEncyclopedia ofReagents forOrganicSynthesis, 2007, http://dx.doi.org/10.1002/047084289X.rc050.pub2.
36. [36]
  [31] K.P. Nandre, V.S. Patil, S.V. Bhosale, CsF mediated rapid condensation of 1,3-cyclohexadione with aromatic aldehydes:comparative study of conventional heating vs. ambient temperature, Chin. Chem. Lett. 22(2011) 777-780.
37. [37]
  [32] (a) Y.A. Tayade, D.R. Patil, Y.B. Wagh, et al., An efficient synthesis of 3-indolyl-3-hydroxy oxindoles and 3,3-di(indolyl)indolin-2-ones catalyzed by sulfonated β-CD as a supramolecular catalyst in water, Tetrahedron Lett. 56(2015) 666-673;
38. [38]
  (b) A.D. Jangale, P.K. Kumavat, Y.B. Wagh, et al., Green process development for the synthesis of aliphatic symmetrical N,N'-disubstituted thiourea derivatives in aqueous medium, Synth. Commun. 45(2015) 236-244;
39. [39]
  (c) D.R. Patil, Y.B. Wagh, P.G. Ingole, et al., β-Cyclodextrin-mediated highly efficient[2+3] cycloaddition reactions for the synthesis of 5-substituted 1Htetrazoles, New J. Chem. 37(2013) 3261-3270;
40. [40]
  (d) D.R. Patil, D.S. Dalal, Biomimetic approach for the synthesis of N,N'-diarylsubstituted formamidines catalyzed by β-cyclodextrin in water, Chin. Chem. Lett. 23(2012) 1125-1130.
41. [41]
  [33] K.M. Khan, I. Khan, S. Perveen, et al., A rapid and efficient CsF catalyzed tandem Knoevenagel-Michael reaction, J. Fluor. Chem. 158(2014) 1-5.
1. [1]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
2. [2]
  Rong-Nan Yi , Wei-Min He . Photocatalytic Minisci-type multicomponent reaction for the synthesis of 1-(halo)alkyl-3-heteroaryl bicyclo[1.1.1]pentanes. Chinese Chemical Letters, 2024, 35(10): 110115-. doi: 10.1016/j.cclet.2024.110115
3. [3]
  Mei Peng , Wei-Min He . Photochemical synthesis and group transfer reactions of azoxy compounds. Chinese Chemical Letters, 2024, 35(8): 109899-. doi: 10.1016/j.cclet.2024.109899
4. [4]
  Shengkai Li , Yuqin Zou , Chen Chen , Shuangyin Wang , Zhao-Qing Liu . Defect engineered electrocatalysts for C–N coupling reactions toward urea synthesis. Chinese Chemical Letters, 2024, 35(8): 109147-. doi: 10.1016/j.cclet.2023.109147
5. [5]
  Yi Luo , Lin Dong . Multicomponent remote C(sp²)-H bond addition by Ru catalysis: An efficient access to the alkylarylation of 2H-imidazoles. Chinese Chemical Letters, 2024, 35(10): 109648-. doi: 10.1016/j.cclet.2024.109648
6. [6]
  Dongdong YANG , Jianhua XUE , Yuanyu YANG , Meixia WU , Yujia BAI , Zongxuan WANG , Qi MA . Design and synthesis of two coordination polymers for the rapid detection of ciprofloxacin based on triphenylpolycarboxylic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2466-2474. doi: 10.11862/CJIC.20240266
7. [7]
  Mianling Yang , Meehyein Kim , Peng Zhan . Modular miniaturized synthesis and in situ biological evaluation facilitate rapid discovery of potent MraY inhibitors as antibacterial agents. Chinese Chemical Letters, 2025, 36(2): 110455-. doi: 10.1016/j.cclet.2024.110455
8. [8]
  Wei-Tao Dou , Qing-Wen Zeng , Yan Kang , Haidong Jia , Yulian Niu , Jinglong Wang , Lin Xu . Construction and application of multicomponent fluorescent droplets. Chinese Chemical Letters, 2025, 36(1): 109995-. doi: 10.1016/j.cclet.2024.109995
9. [9]
  Xiao-Ya Yuan , Cong-Cong Wang , Bing Yu . Recent advances in FeCl₃-photocatalyzed organic reactions via hydrogen-atom transfer. Chinese Chemical Letters, 2024, 35(9): 109517-. doi: 10.1016/j.cclet.2024.109517
10. [10]
  Ruofan Yin , Zhaoxin Guo , Rui Liu , Xian-Sen Tao . Ultrafast synthesis of Na₃V₂(PO₄)₃ cathode for high performance sodium-ion batteries. Chinese Chemical Letters, 2025, 36(2): 109643-. doi: 10.1016/j.cclet.2024.109643
11. [11]
  Anqiu LIU , Long LIN , Dezhi ZHANG , Junyu LEI , Kefeng WANG , Wei ZHANG , Junpeng ZHUANG , Haijun HAO . Synthesis, structures, and catalytic activity of aluminum and zinc complexes chelated by 2-((2,6-dimethylphenyl)amino)ethanolate. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 791-798. doi: 10.11862/CJIC.20230424
12. [12]
  Bin Dong , Ning Yu , Qiu-Yue Wang , Jing-Ke Ren , Xin-Yu Zhang , Zhi-Jie Zhang , Ruo-Yao Fan , Da-Peng Liu , Yong-Ming Chai . Double active sites promoting hydrogen evolution activity and stability of CoRuOH/Co₂P by rapid hydrolysis. Chinese Chemical Letters, 2024, 35(7): 109221-. doi: 10.1016/j.cclet.2023.109221
13. [13]
  Ya-Nan Yang , Zi-Sheng Li , Sourav Mondal , Lei Qiao , Cui-Cui Wang , Wen-Juan Tian , Zhong-Ming Sun , John E. McGrady . Metal-metal bonds in Zintl clusters: Synthesis, structure and bonding in [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–. Chinese Chemical Letters, 2024, 35(8): 109048-. doi: 10.1016/j.cclet.2023.109048
14. [14]
  Caili Yang , Tao Long , Ruotong Li , Chunyang Wu , Yuan-Li Ding . Pseudocapacitance dominated Li₃VO₄ encapsulated in N-doped graphene via 2D nanospace confined synthesis for superior lithium ion capacitors. Chinese Chemical Letters, 2025, 36(2): 109675-. doi: 10.1016/j.cclet.2024.109675
15. [15]
  Hong-Tao Ji , Yu-Han Lu , Yan-Ting Liu , Yu-Lin Huang , Jiang-Feng Tian , Feng Liu , Yan-Yan Zeng , Hai-Yan Yang , Yong-Hong Zhang , Wei-Min He . Nd@C₃N₄-photoredox/chlorine dual catalyzed synthesis and evaluation of antitumor activities of 4-alkylated sulfonyl ketimines. Chinese Chemical Letters, 2025, 36(2): 110568-. doi: 10.1016/j.cclet.2024.110568
16. [16]
  Shehla Khalid , Muhammad Bilal , Nasir Rasool , Muhammad Imran . Photochemical reactions as synthetic tool for pharmaceutical industries. Chinese Chemical Letters, 2024, 35(9): 109498-. doi: 10.1016/j.cclet.2024.109498
17. [17]
  Ying Li , Long-Jie Wang , Yong-Kang Zhou , Jun Liang , Bin Xiao , Ji-Shen Zheng . An improved installation of 2-hydroxy-4-methoxybenzyl (iHmb) method for chemical protein synthesis. Chinese Chemical Letters, 2024, 35(5): 109033-. doi: 10.1016/j.cclet.2023.109033
18. [18]
  Zhixiang Li , Zhirong Yang , Chang Yao , Bin Wu , Gang Qian , Xuezhi Duan , Xinggui Zhou , Jing Zhang . Efficient continuous synthesis of 2-hydroxycarbazole and 4-hydroxycarbazole in a millimeter scale photoreactor. Chinese Chemical Letters, 2024, 35(4): 108893-. doi: 10.1016/j.cclet.2023.108893
19. [19]
  Juanjuan Wang , Fang Wang , Bin Qin , Yue Wu , Huan Yang , Xiaolong Li , Lanfang Wang , Xiufang Qin , Xiaohong Xu . Controlled synthesis and excellent magnetism of ferrimagnetic NiFe₂Se₄ nanostructures. Chinese Chemical Letters, 2024, 35(11): 109449-. doi: 10.1016/j.cclet.2023.109449
20. [20]
  Liyong Ding , Zhenhua Pan , Qian Wang . 2D photocatalysts for hydrogen peroxide synthesis. Chinese Chemical Letters, 2024, 35(12): 110125-. doi: 10.1016/j.cclet.2024.110125

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(670)
HTML views(0)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142