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

Yogesh B. Wagh Yogesh A. Tayade Swapnil A. Padvi Bhupesh S. Patil Nilesh B. Patil Dipak S. Dalal

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

    通讯作者: Dipak S. Dalal,
  • 基金项目:

    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.)

摘要: 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.

English

  • 
    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.[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] 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.[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] 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.[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] R. Baharfar, S.M. Baghbanian, Synthesis of novel uracil based 2,5-diaminofurans using multi-component reactions, Chin. Chem. Lett. 23(2012) 677-680.[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] 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.[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] 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.[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] 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.[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] (a) H. Hong, L.J. Huang, D.W. Teng, A spirocyclic oxindole analogue:synthesis and antitumor activities, Chin. Chem. Lett. 22(2011) 1009-1012;[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.(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. [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.[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. [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.[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. [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;[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.(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. [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.[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. [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.[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. [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.[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. [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.[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. [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.[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. [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.[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. [18] (a) N. Azizi, S. Dezfooli, M.M. Hashemi, Synthesis of spirooxindole in deep eutectic solvent, J. Mol. Liq. 194(2014) 62-67;[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;(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;(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.(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. [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.[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. [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.[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. [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.[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. [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.[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. [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.[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. [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.[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. [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.[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. [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.[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. [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.[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. [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.[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. [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.[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. [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.[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. [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.[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. [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;[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;(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;(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.(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. [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.[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.

  • 加载中
计量
  • PDF下载量:  0
  • 文章访问数:  1019
  • HTML全文浏览量:  1
文章相关
  • 发布日期:  2015-06-17
  • 收稿日期:  2015-03-13
  • 网络出版日期:  2015-05-18
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

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章