Recent Advances on Design and Synthesis of Chiral Imidazolium Ionic Liquids and their Applications in Green Asymmetric Synthesis

Authors

  • Arijit Saha Department of Chemistry, Guru Ghasidas Vishwavidyalaya A Central University
  • Soumen Payra Department of Chemistry, Guru Ghasidas Vishwavidyalaya A Central University
  • Subhash Banerjee Department of Chemistry, Guru Ghasidas Vishwavidyalaya A Central University

DOI:

https://doi.org/10.6000/1929-5030.2016.05.01.1

Keywords:

Chiral Imidazolium Ionic Liquids, Chiral Catalyst and Reaction Medium, Green Asymmetric Synthesis, Recyclable Homogeneous Catalyst, Solvent-free Clean Synthesis.

Abstract

Over the past decade, catalysis by ionic liquids (ILs) has experienced a tremendous growth in the context of “Green Chemistryâ€, and there are numerous examples of a variety of catalytic reactions that have been successfully carried out in such neoteric media.The great enthusiasm for catalysis in ILs is not only driven by the curiosity of chemists, but also due to the growing awareness of developing greener reactions or process media in catalytic science and greener catalytic technologies due their advantages of unique physical and chemical properties as compared to traditional volatile organic solvents.Recently, development of chiral ionic liquids and their applications in asymmetric synthesis have attracted much attention as these reactions have widespread applications in the synthesis of chiral drugs and pharmaceutical industries. Asymmetric induction is mainly achieved by the use of chiral substrates or reagents, chiral catalysts or enzymes. Owing to the vast number of structurally different room temperature ILS that have been synthesized, this review focuses on imidazolium ionic liquids that possess chirality either in the imidazolium moiety or in the anion moiety. The aim of this review is to highlight the recent breakthrough of Chiral ILs in chirality transfer or chiral recognition when used as solvent or co-solvent: the case of task specific ionic liquids is beyond the scope of this review. In the first part, the synthesis of of CILs has been presented and the second part of the review has been devoted on the applications of such CILs in green asymmetric synthesis as well as various pharmaceutical industries.

References


[1] Rogers RD, Seddon KR. Ionic Liquids; Industrial applications to Green Chemistry. ACS symposium series 2002; 488.
[2] Freemantle M. Designer Solvents. Chem Eng News 1998; 76: 32-7. http://dx.doi.org/10.1021/cen-v076n013.p032
[3] Walden P. Molecular weights and electrical conductivity of several fused salts. Bull Acad Imper Sci (St. Petersburg) 1914; 8: 405-22.
[4] (a) Parvulescu VI, Hardacre C. Catalysis in ionic liquids. Chem Rev 2007; 107: 2615-65. http://dx.doi.org/10.1021/cr050948h (b) Rantwijk F, Sheldon RA. Biocatalysis in ionic liquids. Chem Rev 2007; 107: 2757-85. http://dx.doi.org/10.1021/cr050946x (c) Welton T. Room-temperature ionic liquids. solvents for synthesis and catalysis. Chem Rev 1999; 99: 2071-84. http://dx.doi.org/10.1021/cr980032t
[5] (a) Pegot B, Vo-Thanh G, Gori D, Loupy A. First application of chiral ionic liquids in asymmetric Baylis-Hillman reaction. Tetrahedron Lett 2004; 45: 6425-8. http://dx.doi.org/10.1016/j.tetlet.2004.06.134 (b) Ding J, Desikan V, Han X, et al. Use of Chiral Ionic Liquids as solvents for the enantioselective photoisomerization of dibenzobicyclo
[2.2.2]octatrienes. Org Lett 2005; 7: 335. http://dx.doi.org/10.1021/ol047599i (c) Wang Z, Wang Q, Zhang Y, Bao W. Synthesis of new chiral ionic liquids from natural acids and their applications in enantioselective Michael addition. Tetrahedron Lett 2005; 46: 4657-60. http://dx.doi.org/10.1016/j.tetlet.2005.04.134 (d) Luo S, Mi X, Zhang L, Liu S, Xu H, Cheng JP. Functionalized chiral ionic liquids as highly efficient asymmetric organocatalysts for michael addition to nitroolefins. Angew Chem Int Ed 2006; 45: 3093-7. http://dx.doi.org/10.1002/anie.200600048 (e) Gausepohl R, Buskens P, Kleinen J, et al. Highly enantioselective Aza-Baylis-Hillman reaction in a chiral reaction medium. Angew Chem Int Ed 2006; 45: 3689-92. http://dx.doi.org/10.1002/anie.200600327 (f) Branco LC, Gois PMP, Lourenço NMT, Kurteva VB, Afonso CAM. Simple transformation of crystalline chiral natural anions to liquid medium and their use to induce chirality. Chem Commun 2006; 2371-2. http://dx.doi.org/10.1039/b600816j (g) Malhotra SV, Wang Y. Application of chiral ionic liquids in the copper catalyzed enantioselective 1,4-addition of diethylzinc to enones. Tetrahedron: Asymmetry 2006; 17: 1032-5. http://dx.doi.org/10.1016/j.tetasy.2006.03.030 (h) Padar P, Bokros A, Paragi G, et al. Single diastereomers of polyhydroxylated 9-Oxa-1-azabicyclo
[4.2.1]nonanes from intramolecular 1,3-dipolar cycloaddition of -unsaturated nitrones. J Org Chem 2006; 71: 8669-72. http://dx.doi.org/10.1021/jo061503b (i) Pegot B, Nguyen VBO, Gori D, Vo-Thanh G. Asymmetric aza-Diels-Alder reaction of Danishefsky's diene with imines in a chiral reaction medium. Beilstein J Org Chem 2006; 2: 18. http://dx.doi.org/10.1186/1860-5397-2-18 (j) Ni B, Zhang Q, Headley AD. Functionalized chiral ionic liquid as recyclable organocatalyst for asymmetric Michael addition to nitrostyrenes. Green Chem 2007; 9: 737-9. http://dx.doi.org/10.1039/b702081c (l) Nguyen VBO, Vo-Thanh G. Synthesis of novel chiral ammonium-based ionic liquids derived from isosorbide and their applications in an asymmetric Aza Diels-Alder reaction. Lett Org Chem 2007; 4: 158-67. http://dx.doi.org/10.2174/157017807780737219 (m) Yadav LDS, Rai A, Rai V, Awasthi C. Chiral ionic liquidcatalyzed Biginelli reaction: stereoselective synthesis of polyfunctionalized perhydropyrimidines. Tetrahedron 2008; 64: 1420-90. http://dx.doi.org/10.1016/j.tet.2007.11.044 (n) Baudequin C, Bregeon DJ, Levillain J, Guillen F, Plaquevent JC, Gaumont AC. Chiral ionic liquids, a renewal for the chemistry of chiral solvents? Design, synthesis and applications for chiral recognition and asymmetric synthesis. Tetrahedron: Asymmetry 2005; 16: 3921-45. http://dx.doi.org/10.1016/j.tetasy.2005.10.026 (o) Ding J, Armstrong DW. Chiral ionic liquids: synthesis and applications. Chirality 2005; 17: 281-92. http://dx.doi.org/10.1002/chir.20153 (p) Chen X, Li X, Hu A, Wang F. Advances in chiral ionic liquids derived from natural amino acids. Tetrahedron: Asymmetry 2008; 19: 1-14. http://dx.doi.org/10.1016/j.tetasy.2007.11.009 (q) Wang Z, Wang Q, Zhang Y, Bao W. Synthesis of new chiral ionic liquids from natural acids and their applications in enantioselective Michael addition. Tetrahedron Lett 2005; 46: 4657-660. http://dx.doi.org/10.1016/j.tetlet.2005.04.134 (r) Schulz PS, Muller N, Bosmann A, Wasserscheid P. Effective chirality transfer in ionic liquids through ion-pairing effects. Angew Chem Int Ed 2007; 46: 1293-5. http://dx.doi.org/10.1002/anie.200604406
[6] Earle MJ, McCormac PB, Seddon KR. Diels–Alder reactions in ionic liquids. A safe recyclable alternative to lithium perchlorate–diethyl ether mixtures. Green Chem 1999; 1: 23- 5. http://dx.doi.org/10.1039/a808052f
[7] Fukumoto K, Yoshizawa M, Ohno H. Room temperature ionic liquids from 20 natural amino acids. J Am Chem Soc 2005; 127: 2398-9. http://dx.doi.org/10.1021/ja043451i
[8] Fukumoto K, Ohno H. Design and synthesis of hydrophobic and chiral anions from amino acids as precursor for functional ionic liquids. Chem Commun 2006; 3081-3. http://dx.doi.org/10.1039/b606613e
[9] Ding J, Desikan V, Han X, et al. Use of chiral ionic liquids as solvents for the enantioselective photoisomerization of dibenzobicyclo
[2.2.2]octatrienes. Org Lett 2005; 7: 335-7. http://dx.doi.org/10.1021/ol047599i
[10] Bao W, Wang Z, Li Y. Synthesis of chiral ionic liquids from natural amino acids. J Org Chem 2003; 68: 591-3. http://dx.doi.org/10.1021/jo020503i
[11] Genisson Y, Lauth-de Viguerie N, Andre C, Baltas M, Gorrichon L. New chiral imidazolinic derivatives. Tetrahedron: Asymmetry 2005; 16: 1017-23. http://dx.doi.org/10.1016/j.tetasy.2005.01.014
[12] Kim EJ, Ko SY, Dziadulewicz EK. Mitsunobu alkylation of imidazole: a convenient route to chiral ionic liquids. Tetrahedron Lett 2005; 46: 631-3. http://dx.doi.org/10.1016/j.tetlet.2004.11.144
[13] Machado MY, Dorta R. Synthesis and characterization of chiral imidazolium salts. Synthesis 2005; 2473-5.
[14] Tosoni M, Laschat S, Baro A. Synthesis of novel chiral ionic liquids and their phase behavior in mixtures with smectic and nematic liquid crystals. Helv Chim Acta 2004; 87: 2742-9. http://dx.doi.org/10.1002/hlca.200490247
[15] Luo SP, Xu DQ, Yue HD, Wang LP, Yang WL, Xu ZY. Synthesis and properties of novel chiral-amine-functionalized ionic liquids. Tetrahedron: Asymmetry 2006; 17: 2028-33. http://dx.doi.org/10.1016/j.tetasy.2006.07.018
[16] Ni B, Headley AD, Li G. Design and synthesis of C-2 substituted chiral imidazolium ionic liquids from amino acid derivatives. J Org Chem 2005; 70: 10600-2. http://dx.doi.org/10.1021/jo051888i
[17] Ou WH, Huang ZZ. Retracted article: An efficient and practical synthesis of chiral imidazolium ionic liquids and their application in an enantioselective Michael reaction. Green Chem 2006; 8: 731-4. http://dx.doi.org/10.1039/b604801c
[18] Luo S, Mi X, Zhang L, Liu S, Xu H, Cheng JP. Functionalized chiral ionic liquids as highly efficient asymmetric organocatalysts for Michael addition to nitroolefins. Angew Chem Int Ed 2006; 45: 3093-7. http://dx.doi.org/10.1002/anie.200600048
[19] Miao W, Chan TH. Ionic-liquid-supported organocatalyst: efficient and recyclable ionic-liquid-anchored proline for asymmetric Aldol reaction. Adv Synth Catal 2006; 348: 1711- 8. http://dx.doi.org/10.1002/adsc.200606059
[20] Guillen F, Brégeon D, Plaquevent J-C. (S)-Histidine: the ideal precursor for a novel family of chiral aminoacid and peptidic ionic liquids. Tetrahedron Lett 2006; 47: 1245-8. http://dx.doi.org/10.1016/j.tetlet.2005.12.090
[21] Ni B, Zhang Q, Headley AD. Functionalized chiral ionic liquid as recyclable organocatalyst for asymmetric Michael addition to nitrostyrenes. Green Chem 2007; 9: 737-9. http://dx.doi.org/10.1039/b702081c
[22] Seebach D, Oei HA. Mechanism of electrochemical pinacolization. the first asymmetric synthesis in a chiral medium. Angew Chem Int Ed Engl 1975; 14: 634-6. http://dx.doi.org/10.1002/anie.197506342
[23] Wang Z, Wang Q, Zhang Y, Bao W. Synthesis of new chiral ionic liquids from natural acids and their applications in enantioselective Michael addition. Tetrahedron Lett 2005; 46: 4657-60. http://dx.doi.org/10.1016/j.tetlet.2005.04.134
[24] Kiss L, Kurtan T, Antus S, Brunner H. Further insight into the mechanism of Heck oxyarylation in the presence of chiral ligands. Arkivoc 2003; 5: 69-76.
[25] (a) Jarvo ER, Miller SJ. Amino acids and peptides as asymmetric organocatalysts. Tetrahedron 2002; 58: 2481-95. http://dx.doi.org/10.1016/S0040-4020(02)00122-9 (b) List B. Proline-catalyzed asymmetric reactions. Tetrahedron 2002; 58: 5573-90. http://dx.doi.org/10.1016/S0040-4020(02)00516-1 (c) List B. Enamine catalysis is a powerful strategy for the catalytic generation and use of carbanion equivalents. Acc Chem Res 2004; 37: 548-57. http://dx.doi.org/10.1021/ar0300571 (d) Dalko PI, Moisan L. In the golden age of organocatalysis. Angew Chem Int Ed 2004; 43: 5138-75. http://dx.doi.org/10.1002/anie.200400650 (e) Notz W, Tanaka F, Barbas CF. Enamine-based organocatalysis with proline and diamines: the development of direct catalytic asymmetric Aldol, Mannich, Michael, and Diels Alder reactions. Acc Chem Res 2004; 37: 580-91. http://dx.doi.org/10.1021/ar0300468 (f) Lelais G, MacMillan DWC. Asymmetric synthesis enabled by metal-free catalysis. Aldrichimica Acta 2006; 39: 79-87.
[26] Lombardo M, Pasi F, Easwar S, Trombini C. An improved protocol for the direct asymmetric Aldol reaction in ionic liquids, catalysed by onium ion-tagged prolines. Adv Synth Catal 2007; 349: 2061-5. http://dx.doi.org/10.1002/adsc.200700136
[27] Lombardo M, Pasi F, Easwar S, Trombini C. Direct asymmetric Aldol reaction catalyzed by an imidazoliumtagged trans-4-hydroxy-L-proline under aqueous biphasic conditions. Synlett 2008; 2471-4. http://dx.doi.org/10.1055/s-2008-1078055
[28] Lombardo M, Pasi F, Easwar S, Trombini C. The ion tag strategy as a route to highly efficient organocatalysts for the direct asymmetric Aldol reaction. Adv Synth Catal 2009; 351: 276-82. http://dx.doi.org/10.1002/adsc.200800608
[29] Siyutkin DE, Kucherenko AS, Struchkova MI, Zlotin SG. A novel (S)-proline-modified task-specific chiral ionic liquid-an amphiphilic recoverable catalyst for direct asymmetric aldol reactions in water. Tetrahedron Lett 2008; 49: 1212-6. http://dx.doi.org/10.1016/j.tetlet.2007.12.044
[30] Siyutkin DE, Kucherenko AS, Zlotin SG. Hydroxy--amino acids modified by ionic liquid moieties: recoverable organocatalysts for asymmetric aldol reactions in the presence of water. Tetrahedron 2009; 65: 1366-72. http://dx.doi.org/10.1016/j.tet.2008.12.045
[31] Howarth J, Hanlon K, Fayne D, McCormac P. moisture stable dialkylimidazolium salts as heterogeneous and homogeneous lewis acids in the diels-alder reaction. Tetrahedron Lett 1997; 38: 3097-100. http://dx.doi.org/10.1016/S0040-4039(97)00554-6
[32] Janus E, Goc-Maciejewska I, Lozynski M, Pernak J. Diels– Alder reaction in protic ionic liquids. Tetrahedron Lett 2006; 47: 4079-83. http://dx.doi.org/10.1016/j.tetlet.2006.03.172
[33] Van BN, Aupoix A, Vo-Thanh G. Synthesis of novel chiral imidazolium-based ionic liquids derived from isosorbide and their applications in asymmetric aza Diels–Alder reaction. Tetrahedron 2009; 65: 2260-5. http://dx.doi.org/10.1016/j.tet.2009.01.055
[34] Doherty S, Goodrich P, Hardacre C, et al. Recyclable copper catalysts based on imidazolium-tagged bis(oxazolines): a marked enhancement in rate and enantioselectivity for Diels– Alder reactions in ionic liquid. Adv Synth Catal 2007; 349: 951-63. http://dx.doi.org/10.1002/adsc.200600531
[35] Zheng X, Qian Y, Wang Y. Direct asymmetric aza Diels– Alder reaction catalyzed by chiral 2-pyrrolidinecarboxylic acid ionic liquid. Catal Commun 2010; 11: 567-70. http://dx.doi.org/10.1016/j.catcom.2009.12.021
[36] Schulz PS, Mueller N, Boesmann A, Wasserscheid P. Effective chirality transfer in ionic liquids through ion-pairing effects. Angew Chem IntEd Engl 2007; 46: 1293-5. http://dx.doi.org/10.1002/anie.200604406
[37] Natalia AL, Alexandr SK, Dmitry ES, Sergei GZ. (S)- Threonine/,-(S)-diphenylvalinol-derived chiral ionic liquid: an immobilized organocatalyst for asymmetric syn-aldol. Tetrahedron 2011; 67: 1948-54. http://dx.doi.org/10.1016/j.tet.2011.01.017 R

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Published

2016-01-25

How to Cite

Saha, A., Payra, S., & Banerjee, S. (2016). Recent Advances on Design and Synthesis of Chiral Imidazolium Ionic Liquids and their Applications in Green Asymmetric Synthesis. Journal of Applied Solution Chemistry and Modeling, 5(1), 3–20. https://doi.org/10.6000/1929-5030.2016.05.01.1

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