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Inherently chiral calixarenes: a decade’s review

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Abstract

Inherently chiral calixarenes are receiving increasing attention due to their intriguing structures and potential applications in chemical, analytical, biological and material fields. This review mainly covers the advances in syntheses, structures, and applications of inherently chiral calixarenes which emerged later than 2000. Outlook on the development orientation of inherently chiral calixarenes is tentatively provided.

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References

  1. Sirit, A., Yilmaz, M.: Chiral calixarenes. Turk. J. Chem. 33, 159–200 (2009)

    CAS  Google Scholar 

  2. Gopalsamuthiram, V., Predeus, A.V., Huang, R.H., Wulff, W.D.: Optically active calixarenes conduced by methylene substitution. J. Am. Chem. Soc. 131, 18018–18019 (2009)

    Article  CAS  Google Scholar 

  3. Gopalsamuthiram, V., Huang, R., Wulff, W.D.: The synthesis of optically active calix[4]arenes with one or three substituents on the methylene bridges. Chem. Commun. 46, 8213–8215 (2010)

    Article  CAS  Google Scholar 

  4. Böhmer, V., Kraft, D., Tabatabai, M.: Inherently chiral calixarenes. J. Incl. Phenom. Mol. Recognit. Chem. 19, 17–39 (1994)

    Article  Google Scholar 

  5. Cort, A.D., Mandolini, L., Pasquini, C., Schiaffino, L.: “Inherent chirality” and curvature. New J. Chem. 28, 1198–1199 (2004)

    Article  Google Scholar 

  6. Szumna, A.: Inherently chiral concave molecules—from synthesis to applications. Chem. Soc. Rev. 39, 4274–4285 (2010)

    Article  CAS  Google Scholar 

  7. Seeber, G., Tiedemann, B.E.F., Raymond, K.N.: Supramolecular chirality in coordination chemistry. Top. Curr. Chem. 265, 147–183 (2006)

    Article  CAS  Google Scholar 

  8. Rebek Jr, J.: Host–guest chemistry of calixarene capsules. Chem. Commun. 36, 637–643 (2000)

    Article  Google Scholar 

  9. Mateos-Timoneda, M.A.: Supramolecular chirality of self-assembled systems in solution. Chem. Soc. Rev. 33, 363–372 (2004)

    Article  CAS  Google Scholar 

  10. Vázquez-Campos, S., Crego-Calama, M., Reinhoudt, D.N.: Supramolecular chirality of hydrogen-bonded rosette assemblies. Supramol. Chem. 19, 95–106 (2007)

    Article  Google Scholar 

  11. Rudzevich, Y., Rudzevich, V., Böhmer, V.: Selective dimerisation of tetraurea calix[4]arenes. Supramol. Chem. 22, 717–725 (2010)

    Article  CAS  Google Scholar 

  12. Le Poul, N., Douziech, B., Zeitouny, J., Thiabaud, G., Colas, H., Conan, F., Cosquer, N., Jabin, I., Lagrost, C., Hapiot, P., Reinaud, O., Le Mest, Y.: Mimicking the protein access channel to a metal center: effect of a funnel complex on dissociative versus associative copper redox chemistry. J. Am. Chem. Soc. 131, 17800–17807 (2009)

    Article  CAS  Google Scholar 

  13. Kubo, Y., Maeda, S., Tokita, S., Kubo, M.: Colorimetric chiral recognition by a molecular sensor. Nature 382, 522–524 (1996)

    Article  CAS  Google Scholar 

  14. Liu, S., Sandoval, C.A.: Evaluation of calix[4]arene-based chiral diphosphite ligands in Rh-catalyzed asymmetric hydrogenation of simple dehydroamino acid derivatives. J. Mol. Catal. A Chem. 325, 65–72 (2010)

    Article  CAS  Google Scholar 

  15. Krawinkler, K.H., Maier, N.M., Ungaro, R., Sansone, F., Casnati, A., Lindner, W.: Novel cinchona carbamate selectors with complementary enantioseparation characteristics for N-acylated amino acids. Chirality 15, S17–S29 (2003)

    Article  CAS  Google Scholar 

  16. Zheng, Y.S., Zhang, C.: Exceptional chiral recognition of racemic carboxylic acids by calix[4]arenes bearing optically pure α, β-amino alcohol groups. Org. Lett. 6, 1189–1192 (2004)

    Article  CAS  Google Scholar 

  17. Salem, A.B., Regnouf-de-Vains, J.-B.: Synthesis and characterisation of a new pod and based on a calixarene and a β-lactam. Tetrahedron Lett. 42, 7033–7036 (2001)

    Article  Google Scholar 

  18. Ludwig, R.: Calixarenes for biochemical recognition and separation. Microchim. Acta 152, 1–19 (2005)

    Article  CAS  Google Scholar 

  19. Sansone, F., Baldini, L., Casnati, A., Ungaro, R.: Calixarenes: from biomimetic receptors to multivalent ligands for biomolecular recognition. New J. Chem. 34, 2715–2728 (2010)

    Article  CAS  Google Scholar 

  20. Otsuka, H., Shinkai, S.: Stereochemical control of calixarenes useful as rigid and conformationally diversiform platforms for molecular design. Supramol. Sci. 3, 189–205 (1996)

    Article  Google Scholar 

  21. Vysotsky, M., Schmidt, C., Böhmer, V.: Chirality in calixarenes and calixarene assemblies. In: Gokel, G.W. (ed.) Advances in Supramolecular Chemistry, vol. 7, pp. 139–233. JAI Press, Stanford (2000)

    Google Scholar 

  22. Cherenok, S., Dutasta, J.-P., Kalchenko, V.: Phosphorus-containing chiral macrocycles. Curr. Org. Chem. 10, 2307–2331 (2006)

    Article  CAS  Google Scholar 

  23. McIldowie, M.J., Mocerino, M., Ogden, M.I.: A brief review of Cn-symmetric calixarenes and resorcinarenes. Supramol. Chem. 22, 13–39 (2010)

    Article  CAS  Google Scholar 

  24. No, K.H., Gutsche, C.D.: Calixarenes. 8. Short, stepwise synthesis of p-phenylcalix[4]arene, p-phenyl-p-tert-butylcalix[4]arene, and derived products. J. Org. Chem. 47, 2713–2719 (1982)

    Article  Google Scholar 

  25. Tairov, M.A., Vysotsky, M.O., Kalchenko, O.I., Pirozhenko, V.V., Kalchenko, V.I.: Symmetrical and inherently chiral water-soluble calix[4]arenes bearing dihydroxyphosphoryl groups. J. Chem. Soc., Perkin Trans. 1 31, 1405–1411 (2002)

    Article  Google Scholar 

  26. Cao, Y.-D., Luo, J., Zheng, Q.-Y., Chen, C.-F., Wang, M.-X., Huang, Z.-T.: Preparation of both antipodes of enantiopure inherently chiral calix[4]crowns. J. Org. Chem. 69, 206–208 (2004)

    Article  CAS  Google Scholar 

  27. Luo, J., Zheng, Q.-Y., Chen, C.-F., Huang, Z.-T.: Synthesis and optical resolution of a series of inherently chiral calix[4]crowns with cone and partial cone conformations. Chem. Eur. J. 11, 5917–5928 (2005)

    Article  CAS  Google Scholar 

  28. Luo, J., Zheng, Q.-Y., Chen, C.-F., Huang, Z.-T.: Facile synthesis and optical resolution of inherently chiral fluorescent calix[4]crowns: enantioselective recognition towards chiral leucinol. Tetrahedron 61, 8517–8528 (2005)

    Article  CAS  Google Scholar 

  29. Li, S.-Y., Zheng, Q.-Y., Chen, C.-F., Huang, Z.-T.: Preparation of enantiopure inherently chiral calix[5]arenes. Tetrahedron Asymmetry 16, 641–645 (2005)

    Article  CAS  Google Scholar 

  30. Arnecke, R., Böhmer, V., Ferguson, G., Pappalardo, S.: Inherently chiral derivatives of calix[5]crowns. Tetrahedron Lett. 37, 1497–1500 (1996)

    Article  CAS  Google Scholar 

  31. Gonzalez, J.J., Nieto, P.M., Prados, P., Echavarren, A.M., de Mendoza, J.: Calix[4]arene sulfonates: palladium-catalyzed intermolecular migration of sulfonyl groups and isolation of a calix[4]arene in a chiral 1,2-alternate conformation. J. Org. Chem. 60, 7419–7423 (1995)

    Article  CAS  Google Scholar 

  32. Narumi, F., Yamabuki, W., Hattori, T., Kameyama, H., Miyano, S.: Synthesis and optical resolution of an anti-O,O′-dialkylated calix[4]arene. Chem. Lett. 32, 320–321 (2003)

    Article  CAS  Google Scholar 

  33. Narumi, F., Hattori, T., Yamabuki, W., Kabuto, C., Kameyama, H.: Resolution of inherently chiral anti-O,O′-dialkylated calix[4]arenes and determination of their absolute stereochemistries by CD and X-ray methods. Tetrahedron Asymmetry 16, 793–800 (2005)

    Article  CAS  Google Scholar 

  34. Kleij, A.W., Souto, B., Pastor, C.J., Prados, P., de Mendoza, J.: Unexpected single-step formation of 1,2-anti-heterodisubstituted calix[4]arenes upon alkylation of a tribenzoyl precursor. J. Org. Chem. 68, 8711–8714 (2003)

    Article  CAS  Google Scholar 

  35. Shirakawa, S., Moriyama, A., Shimizu, S.: Design of a novel inherently chiral calix[4]arene for chiral molecular recognition. Org. Lett. 9, 3117–3119 (2007)

    Article  CAS  Google Scholar 

  36. Shirakawa, S., Moriyama, A., Shimizu, S.: Synthesis, optical resolution and enantiomeric recognition ability of novel, inherently chiral calix[4]arenes: trial application to asymmetric reactions as organocatalysts. Eur. J. Org. Chem. 2008, 5957–5964 (2008)

    Article  Google Scholar 

  37. Shirakawa, S., Kimura, T., Murata, S.-i., Shimizu, S.: Synthesis and resolution of a multifunctional inherently chiral calix[4]arene with an ABCD substitution pattern at the wide rim: the effect of a multifunctional structure in the organocatalyst on enantioselectivity in asymmetric reactions. J. Org. Chem. 74, 1288–1296 (2009)

    Article  CAS  Google Scholar 

  38. Shirakawa, S., Shimizu, S.: Synthesis of an inherently chiral calix[4]arene amino acid and its derivatives: their application to asymmetric reactions as organocatalysts. Eur. J. Org. Chem. 2009, 1916–1924 (2009)

    Article  Google Scholar 

  39. Shirakawa, S., Shimizu, S.: Improved design of inherently chiral calix[4]arenes as organocatalysts. New J. Chem. 34, 1217–1222 (2010)

    Article  CAS  Google Scholar 

  40. Colasson, B., Reinaud, O.: Selective hetero-trisfunctionalization of the large rim of a biomimetic calix[6]arene using host–guest chemistry as a synthetic tool. J. Am. Chem. Soc. 130, 15226–15227 (2008)

    Article  CAS  Google Scholar 

  41. Luo, J., Shen, L.-C., Chung, W.-S.: Inherently chiral biscalix[4]arenes: design and syntheses. J. Org. Chem. 75, 464–467 (2010)

    Article  CAS  Google Scholar 

  42. Miao, R., Zheng, Q.-Y., Chen, C.-F., Huang, Z.-T.: Efficient syntheses and resolutions of inherently chiral calix[4]quinolines in the cone and partial-cone conformation. J. Org. Chem. 70, 7662–7671 (2005)

    Article  CAS  Google Scholar 

  43. Miao, R., Xu, Z.-X., Huang, Z.-T., Chen, C.-F.: Enantiopure inherently chiral calix[4]arene derivatives containing quinolin-2-yl-methanol moiety: synthesis and application in the catalytic asymmetric addition of diethylzinc to benzaldehyde. Sci. China B. Chem. 52, 505–512 (2009)

    Article  CAS  Google Scholar 

  44. Mastalerz, M., Hüggenberg, W., Dyker, G.: Photochemistry of styrylcalix[4]arenes. Eur. J. Org. Chem. 2006, 3977–3987 (2006)

    Article  Google Scholar 

  45. Verboom, W., Bodewes, P.J., van Essen, G., Timmerman, P., van Hummel, G.J., Harkema, S., Reinhoudt, D.N.: A novel approach to inherently chiral calix[4]arenes by direct introduction of a substituent at the meta position. Tetrahedron 51, 499–512 (1995)

    Article  CAS  Google Scholar 

  46. Amato, M.E., Ballistreri, F.P., Pappalardo, A., Tomaselli, G.A., Toscano, R.M., Williams, D.J.: Novel chiral (salen)MnIII complexes containing a calix[4]arene unit as catalysts for enantioselective epoxidation reactions of (Z)-aryl alkenes. Eur. J. Org. Chem. 2005, 3562–3570 (2005)

    Article  Google Scholar 

  47. Consoli, G.M.L., Cunsolo, F., Geraci, C., Neri, P.: Synthesis of p-tert-butyl-5,5′-bicalix[4]arene and access to 5,5′-bicalix[4]arenes functionalized at the upper rim. Lett. Org. Chem. 2, 252–257 (2005)

    Article  CAS  Google Scholar 

  48. Troisi, F., Pierro, T., Gaeta, C., Carratù, M., Neri, P.: Appending aromatic moieties at the para- and meta-position of calixarene phenol rings via p-bromodienone route. Tetrahedron Lett. 50, 4416–4419 (2009)

    Article  CAS  Google Scholar 

  49. Pavlov, V.A.: C 2 and C 1 symmetry of chiral auxiliaries in catalytic reactions on metal complexes. Tetrahedron 64, 1147–1179 (2008)

    Article  CAS  Google Scholar 

  50. Ikeda, A., Yoshimura, M., Lhoták, P., Shinkai, S.: Synthesis and optical resolution of naphthalene-containing inherently chiral calix[4]arenes derived by intramolecular ring closure or stapling of proximal phenyl units. J. Chem. Soc. Perkin Trans. 1 25, 1945–1950 (1996)

    Article  Google Scholar 

  51. Ikeda, A., Shinkai, S.: ‘Stapled’ calix[n]arenes: immobilization of the calix[4]arene conformation by cross-linking on the upper rim. J. Chem. Soc. Perkin Trans 1 22, 2671–2673 (1993)

    Article  Google Scholar 

  52. Bitter, I., Grün, A., Tóth, G., Balázs, B., Horváth, G., Tőke, L.: Studies on calix(aza)crowns, II. Synthesis of novel proximal doubly bridged calix[4]arenes by intramolecular ring closure of syn 1,3- and 1,2-ω-chloroalkylamides. Tetrahedron 54, 3857–3870 (1998)

    Article  CAS  Google Scholar 

  53. Sharma, S.K., Gutsche, C.D.: Synthesis and reactions of calix[4]arene bisanhydrides. J. Org. Chem. 64, 3507–3512 (1999)

    Article  CAS  Google Scholar 

  54. Kleij, A.W., Prados, P., de Mendoza, J.: A fast access to non-symmetrically substituted 1,3-alternate conformers of calix[4]arenes. Eur. J. Org. Chem. 2004, 2848–2852 (2004)

    Article  Google Scholar 

  55. Shimizu, S., Moriyama, A., Kito, K., Sasaki, Y.: Selective synthesis and isolation of all possible conformational isomers of proximally para-disubstituted calix[4]arene. J. Org. Chem. 68, 2187–2194 (2003)

    Article  CAS  Google Scholar 

  56. Blanda, M.T., Edwards, L., Salazar, R., Boswell, M.: Synthesis and characterization of an inherently chiral calix[6]arene in the 1,4-alternate conformation. Tetrahedron Lett. 47, 7081–7084 (2006)

    Article  CAS  Google Scholar 

  57. Wolff, A., Böhmer, V., Vogt, W., Ugozzoli, F., Andreetti, G.D.: Dissymmetric calix[4]arenes with C 2 and C 4 symmetry. J. Org. Chem. 55, 5665–5667 (1990)

    Article  CAS  Google Scholar 

  58. Chowdhury, S., Georghiou, P.E.: Synthesis and properties of a new member of the calix naphthalene family: a C 2-symmetrical endo-calix[4]naphthalene. J. Org. Chem. 67, 6808–6811 (2002)

    Article  CAS  Google Scholar 

  59. Barton, O.G., Neumann, B., Stammler, H.-G., Mattay, J.: Intramolecular direct arylation in an A, C-functionalized calix[4]arene. Org. Biomol. Chem. 6, 104–111 (2008)

    Article  CAS  Google Scholar 

  60. Dieleman, C., Steyer, S., Jeunesse, C., Matt, D.: Diphosphines based on an inherently chiral calix[4]arene scaffold: synthesis and use in enantioselective catalysis. J. Chem. Soc. Dalton Trans. 30, 2508–2517 (2001)

    Article  Google Scholar 

  61. Yakovenko, A.V., Boyko, V.I., Danylyuk, O., Suwinska, K., Lipkowski, J., Kalchenko, V.I.: Diastereoselective lower rim (1S)-camphor sulfonylation as the shortest way to the inherently chiral calix[4]arene. Org. Lett. 9, 1183–1185 (2007)

    Article  CAS  Google Scholar 

  62. Boyko, V.I., Yakovenko, A.V., Matvieiev, Y.I., Kalchenko, O.I., Shishkin, O.V., Shishkina, S.V., Kalchenko, V.I.: Regio- and stereoselective 1(S)-camphor sulfonylation of monoalkoxycalix[4]arenes. Tetrahedron 64, 7567–7573 (2008)

    Article  CAS  Google Scholar 

  63. Boyko, V.I., Matvieiev, Y.I., Klyachina, M.A., Yesypenko, O.A., Shishkina, S.V., Shishkin, O.V., Kalchenko, V.I.: Proximal heteroalkylation of monoalkoxycalix[4]arenes in synthesis of inherently chiral molecules. Tetrahedron 65, 4220–4227 (2009)

    Article  CAS  Google Scholar 

  64. Boyko, V.I., Shivanyuk, A., Pyrozhenko, V.V., Zubatyuk, R.I., Shishkin, O.V., Kalchenko, V.I.: A stereoselective synthesis of asymmetrically substituted calix[4]arene carbamates. Tetrahedron Lett. 47, 7775–7778 (2006)

    Article  CAS  Google Scholar 

  65. Kliachyna, M.A., Yesypenko, O.A., Pirozhenko, V.V., Shishkina, S.V., Shishkin, O.V., Boyko, V.I., Kalchenko, V.I.: Synthesis, optical resolution and absolute configuration of inherently chiral calixarene carboxylic acids. Tetrahedron 65, 7085–7091 (2009)

    Article  CAS  Google Scholar 

  66. Xu, Z.-X., Zhang, C., Zheng, Q.-Y., Chen, C.-F., Huang, Z.-T.: A new approach to enantiopure inherently chiral calix[4]arenes: determination of their absolute configurations. Org. Lett. 9, 4447–4450 (2007)

    Article  CAS  Google Scholar 

  67. Xu, Z.-X., Zhang, C., Yang, Y., Chen, C.-F., Huang, Z.-T.: Effective nonenzymatic kinetic resolution of racemic m-nitro-substituted inherently chiral aminocalix[4]arenes. Org. Lett. 10, 477–479 (2008)

    Article  CAS  Google Scholar 

  68. Xu, Z.X., Zhang, C., Huang, Z.T., Chen, C.F.: Efficient synthesis and resolution of meta-substituted inherently chiral aminocalix[4]arene derivatives. Chin. Sci. Bull. 55, 2859–2869 (2010)

    Article  Google Scholar 

  69. Xu, Z.-X., Li, G.-K., Chen, C.-F., Huang, Z.-T.: Inherently chiral calix[4]arene-based bifunctional organocatalysts for enantioselective aldol reactions. Tetrahedron 64, 8668–8675 (2008)

    Article  CAS  Google Scholar 

  70. Xu, Z.-X., Huang, Z.-T., Chen, C.-F.: Synthesis and structures of novel enantiopure inherently chiral calix[4]arene-derived salphen ligands and their transition-metal complexes. Tetrahedron Lett. 50, 5430–5433 (2009)

    Article  CAS  Google Scholar 

  71. Herbert, S.A., Arnott, G.E.: An asymmetric ortholithiation approach to inherently chiral calix[4]arenes. Org. Lett. 21, 4986–4989 (2009)

    Article  Google Scholar 

  72. Herbert, S.A., Arnott, G.E.: Synthesis of inherently chiral calix[4]arenes: stereocontrol through ligand choice. Org. Lett. 12, 4600–4603 (2010)

    Article  CAS  Google Scholar 

  73. Itzhak, N., Biali, S.E.: Selective functionalization of a single methylene bridge of a calix[6]arene. J. Org. Chem. 75, 3437–3442 (2010)

    Article  CAS  Google Scholar 

  74. Kogan, K., Biali, S.E.: Incorporation of substituents at the methylene linkages of the calix[5]arene skeleton. J. Org. Chem. 74, 7172–7175 (2009)

    Article  CAS  Google Scholar 

  75. Kogan, K., Columbus, I., Biali, S.E.: Functionalization of the methylene bridges of the calix[6]arene scaffold. J. Org. Chem. 73, 7327–7335 (2008)

    Article  CAS  Google Scholar 

  76. Columbus, I., Biali, S.E.: Calix[4]arene derivatives monosubstituted at all four methylene bridges. J. Org. Chem. 73, 2598–2606 (2008)

    Article  CAS  Google Scholar 

  77. Harvey, P.D.: Wide-rim and outer-face functionalizations of calix[4]arene. Coord. Chem. Rev. 233–234, 289–309 (2002)

    Article  Google Scholar 

  78. Iki, H., Kikuchi, T., Shinkai, S.: Syntheses and spectral characterizations of tricarbonylchromium complexes of calix[4]arenes. J. Chem. Soc. Perkin Trans. 1 22, 205–210 (1993)

    Article  Google Scholar 

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Acknowledgments

The authors are grateful to National Natural Science Foundation of China (No. 20902029, 20872040) and National Innovative Training and Research Program for Undergraduates (2009097) for financial support. Min Zhang (undergraduate) is appreciated for her assistance.

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  1. Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan, 430030, China

    Jun Luo

  2. Department of Chemistry, Huazhong University of Science and Technology, Wuhan, 430074, China

    Yan-Song Zheng

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  1. Yan-Song Zheng
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  2. Jun Luo
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Zheng, YS., Luo, J. Inherently chiral calixarenes: a decade’s review. J Incl Phenom Macrocycl Chem 71, 35–56 (2011). https://doi.org/10.1007/s10847-011-9935-4

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