Chiral pyrrolidinium salts derived from menthol as precursor – synthesis and properties

Janus, Ewa; Gano, Marcin

doi:10.1515/pjct-2017-0054

Abstract

Six new chiral pyrolidinium salts with chiral substituent at quaternary nitrogen atom were synthesized with high overall yields from (-)-menthol as cheap chiral precursor and were identified by NMR and HRMS spectroscopy. It was shown that anion type had the effect on chemical shift of protons adjacent to quaternary nitrogen atom and physical properties of these salts. Salts with NTf₂ or NPf₂ were in a liquid state at room temperature and characterized with the highest thermal stability among others. Furthermore, chiral ionic liquid with NTf₂ anion was used as solvent in Diels-Alder reaction and gave higher yield and stereoselectivity than in ionic liquids with achiral cations. Synthesized chiral salts have the potential as chiral solvents in synthesis and auxiliaries in analytical methods to improve chiral recognition.

References

1. Gadenne, B., Hesemann, P. & Moreau, J.J.E. (2004). Ionic liquids incorporating camphorsulfonamide units for the Ti-promoted asymmetric diethylzinc addition to benzaldehyde. Tetrahedron Lett. 45, 8157–8160. DOI: 10.1016/j.tetlet.2004.09.038.10.1016/j.tetlet.2004.09.038
Open DOI Search in Google Scholar Back to article
2. Singh, A. & Chopra, H.K. (2016). New benzimidazolium-based chiral ionic liquids: synthesis and application in enantioselective sodium borohydride reductions in water. Tetrahedron: Asymmetry 27, 448–453. DOI:10.1016/j.tetasy.2016.04.004.10.1016/j.tetasy.2016.04.004
Open DOI Search in Google Scholar Back to article
3. Vasiloiu, M., Leder, S., Gaertner, P., Mereiter, K. & Bica, K. (2013). Coordinating chiral ionic liquids. Org. Biomol. Chem. 11, 8092. DOI: 10.1039/c3ob41635f.10.1039/c3ob41635f24163003
Open DOI Search in Google Scholar Back to article
4. Bica, K., Gmeiner, G., Reichel, C., Lendl, B. & Gaertner, P. (2007). Microwave-Assisted Synthesis of Camphor-Derived Chiral Imidazolium Ionic Liquids and Their Application in Diastereoselective Diels–Alder Reaction. Synthesis 9, 1333–1338. DOI: 10.1055/s-2007-966018.10.1055/s-2007-966018
Open DOI Search in Google Scholar Back to article
5. Baudequin, C., Bregeon, D., Levillain, J., Guillen, F., Plaquevent, J.C. & Gaumont, A.C. (2005). Chiral ionic liquids, a renewal for the chemistry of chiral solvents? Design, synthesis and applications for chiral recognition and asymmetric synthesis. Tetrahedron: Asymmetry 16, 3921–3945. DOI: 10.1016/j.tetasy.2005.10.026.10.1016/j.tetasy.2005.10.026
Open DOI Search in Google Scholar Back to article
6. Kapnissi-Christodoulou, C.P., Stavrou, I.J. & Mavroudi, M.C. (2014). Chiral ionic liquids in chromatographic and electrophoretic separations. J. Chromatogr. A 1363, 2–10. DOI: 10.1016/j.chroma.2014.05.059.10.1016/j.chroma.2014.05.05924913367
Open DOI Search in Google Scholar Back to article
7. Zhang, Y., Du, S., Feng, Z., Du, Y. & Yan, Z. (2016). Evaluation of synergistic enantioseparation systems with chiral spirocyclic ionic liquids as additives by capillary electrophoresis. Anal. Bioanal. Chem. 408, 2543–2555. DOI: 10.1007/s00216-016-9356-8.10.1007/s00216-016-9356-826894758
Open DOI Search in Google Scholar Back to article
8. Kartsova, L.A., Bessonova, E.A. & Kolobova, E.A. (2016). Ionic Liquids as Modifiers of Chromatographic and Electrophoretic Systems. J. Anal. Chem. 71(2), 141–152. DOI: 10.1134/S1061934816020064.10.1134/S1061934816020064
Search in Google Scholar Back to article
9. Ishida, Y., Sasaki, D., Miyauchi, H. & Saigo, K. (2006). Synthesis and properties of a diastereopure ionic liquid with planar chirality. Tetrahedron Lett. 47, 7973–7976. DOI: 10.1016/j.tetlet.2006.08.101.10.1016/j.tetlet.2006.08.101
Open DOI Search in Google Scholar Back to article
10. Winkel, A. & Wilhelm, R. (2010). New Chiral Ionic Liquids Based on Enantiopure Sulfate and Sulfonate Anions for Chiral Recognition. Eur. J. Org. Chem. 5817–5824. DOI: 10.1002/ejoc.201000801.10.1002/ejoc.201000801
Search in Google Scholar Back to article
11. Santamarta, F., Vilas, M., Tojo, E. & Fall, Y. (2016). Synthesis and properties of novel chiral imidazolium-based ionic liquids derived from carvone. RSC Adv. 6, 31177. DOI: 10.1039/c6ra00654j.10.1039/C6RA00654J
Open DOI Search in Google Scholar Back to article
12. Bwambok, D.K., Marwani, H.M., Fernand, V.E., Fakayode, S.O., Lowry, M., Negulescu, I., Strongin, R. M. & Warner, I.M. (2008). Synthesis and Characterization of Novel Chiral Ionic Liquids and Investigation of their Enantiomeric Recognition Properties. Chirality 20(2), 151–158. DOI: 10.1002/chir.20517.10.1002/chir.20517265042218092298
Open DOI Search in Google Scholar Back to article
13. Kataev, V.E., Strobykina, I.Yu. & Zakharova, L.Ya. (2014). Quaternary ammonium derivatives of natural terpenoids. Synthesis and properties. Russ. Chem. Bull. Int. Ed. 63(9), 1884—1900. DOI: 10.1007/s11172-014-0680-x.10.1007/s11172-014-0680-x
Open DOI Search in Google Scholar Back to article
14. Nageshwar, D., Muralimahan, D.R., Acharyulu, P.V.R. (2009). Terpenes to Ionic Liquids: Synthesis and Characterization of Citronellal-Based Chiral Ionic Liquids. Synthetic Commun. 39, 3357–3368. DOI: 10.1080/00397910902768226.10.1080/00397910902768226
Open DOI Search in Google Scholar Back to article
15. Wang, Y. (2003). Synthesis and application of novel chiral ionic liquids derived from alpha-pinene. M.Sc. thesis. Newark, NJ: New Jersey Institute of Technology, Department Chemistry and Environmental Science.
Search in Google Scholar Back to article
16. Nobuoka, K., Kitaoka, S., Kunimitsu, K., Iio, M., Harran, T., Wakisaka, A. & Ishikawa, Y. (2005). Camphor Ionic Liquid: Correlation between Stereoselectivity and Cation-Anion Interaction. J. Org. Chem. 70, 10106–10108. DOI: 10.1021/jo051669x.10.1021/jo051669x16292848
Open DOI Search in Google Scholar Back to article
17. Santamarta, F., Vilas, M., Tojo, E. & Fall, Y. (2016). Synthesis and properties of novel chiral imidazoliumbased ionic liquids derived from carvone. RSC Adv. 6, 31177–31180. DOI: 10.1039/c6ra00654j.10.1039/C6RA00654J
Open DOI Search in Google Scholar Back to article
18. Matos, R.A.F. & Andrade, C.K.Z. (2008). Synthesis of new chiral ionic liquids based on (-)-menthol and (-)-borneol. Tetrahedron Lett. 49, 1652–1655. DOI: 10.1016/j.tetlet.2008.01.011.10.1016/j.tetlet.2008.01.011
Open DOI Search in Google Scholar Back to article
19. Pernak, J. & Feder-Kubis, J. (2005). Synthesis and Properties of Chiral Ammonium-Based Ionic Liquids. Chem. Eur. J. 11, 4441–4449. DOI: 10.1002/chem.200500026.10.1002/chem.20050002615883984
Open DOI Search in Google Scholar Back to article
20. Feder-Kubis, J. & Pernak, J. (2006). Chiral pyridinium-based ionic liquids containing the (1R,2S,5R) -( )-menthyl group. Tetrahedron: Asymmetry 17, 1728–1737. DOI: 10.1016/j.tetasy.2006.06.014.10.1016/j.tetasy.2006.06.014
Open DOI Search in Google Scholar Back to article
21. Feder-Kubis, J., Kubicki, M. & Pernak, J. (2010). 3-Alkoxymethyl-1-(1R,2S,5R)-( )-menthoxymethylimidazolium salts-based chiral ionic liquids. Tetrahedron: Asymmetry 21, 2709–2718. DOI: 10.1016/j.tetasy.2010.10.029.10.1016/j.tetasy.2010.10.029
Open DOI Search in Google Scholar Back to article
22. Hardcare, Ch., Holbrey, J.D., Nieuwenhuyzen, M., Youngs, T.G.A. (2007). Structure and Solvation in Ionic Liquids. Acc. Chem. Res.40(11), 1146–1155. DOI: 10.1021/ar700068x.10.1021/ar700068x
Open DOI Search in Google Scholar Back to article
23. Bonanni, M., Soldaini, G., Faggi, C., Goti, A. & Cardona, F. (2009). Novel L-Tartaric Acid Derived Pyrrolidinium Cations for the Synthesis of Chiral Ionic Liquids. Synlett 5, 0747–0750. DOI: 10.1055/s-0028-1087950.10.1055/s-0028-1087950
Open DOI Search in Google Scholar Back to article
24. Shi M., Kazuta K., Satoh Y., Masaki Y. (1994). Synthesis and Investigation of C2-Symmetric Optically Active Pyrrolidinium Salts as Chiral Phase-Transfer Catalysts. Chem. Pharm. Bull. 42(12), 2625–2628. DOI: 10.1248/cpb.42.2625.10.1248/cpb.42.2625
Open DOI Search in Google Scholar Back to article
25. Liang, Y., Ling, D., Hu, Z. & Cao, D. (2015). Synthesis and Physicochemical Characterization of Chiral Pyrrolidinium-Based Surfactants. J. Disper. Sci. Technol. 36, 831–837. DOI: 10.1080/01932691.2014.926252.10.1080/01932691.2014.926252
Open DOI Search in Google Scholar Back to article
26. Nobuoka, K., Kitaoka, S., Kojima, T., Kawano, Y., Hirano, K., Tange, M., Obata, S., Yamamoto, Y., Harran, T. & Ishikawa, Y. (2014). Proline Based Chiral Ionic Liquids for Enantioselective Michael Reaction. Org.Chem. Inter.1–9. DOI: 10.1155/2014/836126.10.1155/2014/836126
Open DOI Search in Google Scholar Back to article
27. Raju, C.M.H., Dubey, P.K. & Acharyulu, P.V.R. (2008). Synthesis and Characterization of the First Pyrrolidine-Based Chiral Ionic Liquids. Synt. Commun. 38, 1439–1447. DOI: 10.1080/00397910801916140.10.1080/00397910801916140
Open DOI Search in Google Scholar Back to article
28. Kitazume, T. (2001). Optically Active Ionic Liquids. U.S. Patent No. 20010031875A1. United States Patent Application.
Search in Google Scholar Back to article
29. Fisher, T., Sethi, A., Welton, T. & Woolf, J. (1999). Diels-Alder Reaction in Room-Temperature Ionic Liquids. Tetrahedron Lett. 40, 793–796. DOI: 10.1016/S0040-4039(98)02415-0.10.1016/S0040-4039(98)02415-0
Open DOI Search in Google Scholar Back to article
30. Aggarwal, A., Lancaster, N.L., Sethi, A.R. & Welton, T. (2002). The role of hydrogen binding in controlling the selectivity of Diels-Alder reactions in room-temperature ionic liquids. Green Chem. 4, 517–520. DOI: 10.1039/b206472c.10.1039/b206472c
Open DOI Search in Google Scholar Back to article
31. Janus E., Goc-Maciejewska, I. Łożyński, M. & Pernak, J. (2006). Diels-Alder reaction in protic ionic liquids. Tetrahedron Lett. 47, 4079–4083. DOI: 10.1016/j.tetlet.2006.03.172.10.1016/j.tetlet.2006.03.172
Open DOI Search in Google Scholar Back to article
32. Stefaniak, W., Janus, E. & Milchert, E. (2011). Diels-Alder reaction of cyclopentadiene and alkyl acrylates in the presence of pyrrolidinium ionic liquids with various anions. Catal. Lett. 141, 742–747. DOI: 10.1007/s10562-011-0558-6.10.1007/s10562-011-0558-6
Open DOI Search in Google Scholar Back to article
33. Janus, E., Bittner, B. (2010). Triethylsulfonium bistriflimide as the reaction medium in catalyzed and uncatalyzed cycloaddition [4+2]. Catal. Lett. 134, 147–154. DOI: 10.1007/s10562-009-0211-9.10.1007/s10562-009-0211-9
Open DOI Search in Google Scholar Back to article
34. Janus, E. & Stefaniak, W. (2008). The Diels-Alder reaction in phosphonium ionic liquid catalysed by metal chlorides, triflates and triflimides. Catal. Lett. 124, 105–110. DOI: 10.1007/s10562-008-9431-7.10.1007/s10562-008-9431-7
Open DOI Search in Google Scholar Back to article

Chiral pyrrolidinium salts derived from menthol as precursor – synthesis and properties

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