Cyclotrehalins: Cyclooligosaccharide receptors featuring a hydrophobic cavity

Angewandte Chemie - International Edition

Volumn 41, Issue 19, 2002, Pages 3674-3676

  Benito, Juan M ^b   Jiménez Blanco, José L ^b   Mellet, C Ortiz ^b   García Fernández, José M ^a  

^a INSTITUTO DE INVESTIGACIONES QUÍMICAS   (Spain)

^b UNIVERSITY OF SEVILLE   (Spain)

Author keywords

Carbohydrates; Host guest systems; Oligosaccharides; Receptors

Indexed keywords

CARBOHYDRATES; HYDROPHOBICITY;

CYCLOOLIGOSACCHARIDES;

OLIGOMERS;

CARBOHYDRATE; CARRIER PROTEIN; CYCLODEXTRIN; CYCLOOLIGOSACCHARIDE RECEPTOR; DRUG DERIVATIVE; RECEPTOR; TREHALOSE; UNCLASSIFIED DRUG;

ARTICLE; BINDING SITE; CHEMICAL STRUCTURE; CHEMISTRY; CONFORMATION; CYCLIZATION; HYDROGEN BOND; HYDROPHOBICITY; METABOLISM; MOLECULAR INTERACTION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS;

BINDING SITES; CARBOHYDRATE CONFORMATION; CARRIER PROTEINS; CYCLIZATION; CYCLODEXTRINS; HYDROPHOBICITY; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR STRUCTURE; TREHALOSE;

EID: 0037020362     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20021004)41:19<3674::AID-ANIE3674>3.0.CO;2-F     Document Type: Article

References (27)

1. a) C. R. Bertozzi, L. L. Kiessling, Science 2001, 291, 2357-2364;
2. b) P. Sears, C.-H. Wong, Angew. Chem. 1999, 111, 2446-2471; Angew. Chem. Int. Ed. 1999, 38, 1875-1917;
3. b) P. Sears, C.-H. Wong, Angew. Chem. 1999, 111, 2446-2471; Angew. Chem. Int. Ed. 1999, 38, 1875-1917;
4. c) H. Lis, N. Sharon, Chem. Rev. 1998, 98, 637-674.
5. T. D. James, S. Shinkai, Top. Curr. Chem. 2002, 218, 159-200;
6. a) A. P. Davis, R. S. Wareham, Angew. Chem. 1999, 111, 3160-3179; Angew. Chem. Int. Ed. 1999, 38, 2978-2996.
7. a) A. P. Davis, R. S. Wareham, Angew. Chem. 1999, 111, 3160-3179; Angew. Chem. Int. Ed. 1999, 38, 2978-2996.
8. a) M. V Rekharsky, Y. Inoue, Chem. Rev. 1998, 98, 1875-1917;
9. b) Comprehensive Supramolecular Chemistry, Vol. 2 (Eds.: J. Szejtli, T. Osa), Pergamon, Oxford, 1996.
10. a) G. Gattuso, S. A. Nepogodiev, J. F. Stoddart, Chem. Rev. 1998, 98, 1919-1958.
11. For a recent paper see: b) A. Dondoni, A. Marra, M.-C. Scherrmann, V. Bertolasi, Chem. Eur. J. 2001, 7, 1371-1382.
12. For cyclodextrin analogues having intersaccharide functional groups other than the glycosidic oxygen (sulfur, butadiyne, amide), see: a) L. Bornaghi, J.-P. Utille, D. Penninga, A. K. Schmidt, L. Dijkhuizen, G. E. Schulz, H. Driguez, Chem. Commun. 1996, 2541-2542; b) R. Bürli, A. Vasella, Angew. Chem. 1997, 109, 1945-1946; Angew. Chem. Int. Ed. Engl. 1997, 36, 1852-1853; c) E. Locardi, M. Stöckle, S. Gruner, H. Kessler, J. Am. Chem. Soc. 2001, 123, 8189-8196.
13. For cyclodextrin analogues having intersaccharide functional groups other than the glycosidic oxygen (sulfur, butadiyne, amide), see: a) L. Bornaghi, J.-P. Utille, D. Penninga, A. K. Schmidt, L. Dijkhuizen, G. E. Schulz, H. Driguez, Chem. Commun. 1996, 2541-2542: b) R. Bürli, A. Vasella, Angew. Chem. 1997, 109, 1945-1946; Angew. Chem. Int. Ed. Engl. 1997, 36, 1852-1853; c) E. Locardi, M. Stöckle, S. Gruner, H. Kessler, J. Am. Chem. Soc. 2001, 123, 8189-8196.
14. For cyclodextrin analogues having intersaccharide functional groups other than the glycosidic oxygen (sulfur, butadiyne, amide), see: a) L. Bornaghi, J.-P. Utille, D. Penninga, A. K. Schmidt, L. Dijkhuizen, G. E. Schulz, H. Driguez, Chem. Commun. 1996, 2541-2542: b) R. Bürli, A. Vasella, Angew. Chem. 1997, 109, 1945-1946; Angew. Chem. Int. Ed. Engl. 1997, 36, 1852-1853; c) E. Locardi, M. Stöckle, S. Gruner, H. Kessler, J. Am. Chem. Soc. 2001, 123, 8189-8196.
15. For cyclodextrin analogues having intersaccharide functional groups other than the glycosidic oxygen (sulfur, butadiyne, amide), see: a) L. Bornaghi, J.-P. Utille, D. Penninga, A. K. Schmidt, L. Dijkhuizen, G. E. Schulz, H. Driguez, Chem. Commun. 1996, 2541-2542: b) R. Bürli, A. Vasella, Angew. Chem. 1997, 109, 1945-1946; Angew. Chem. Int. Ed. Engl. 1997, 36, 1852-1853; c) E. Locardi, M. Stöckle, S. Gruner, H. Kessler, J. Am. Chem. Soc. 2001, 123, 8189-8196.
16. For original uses of thiourea groups in host design, see: a) E. Fan, S. A. Van Arman, S. Kincaid, A. D. Hamilton, J. Am. Chem. Soc. 1993, 115, 369-370; b) C. S. Wilcox, E. Kim, D. Romano, L. H. Kuo, A. L. Burt, D. P. Curran, Tetrahedron 1995, 51, 621-634; c) S. Nishizawa, P. Bühlmann, M. Iwao, Y. Umezawa, Tetrahedron. Lett. 1995, 36, 6483-6486; d) G. J. Pernía, J. D. Kilburn, J. W. Essex, R. J. Mortirshire-Smith, M. Rowley, J. Am. Chem. Soc. 1996, 118, 10220-10227.
17. For original uses of thiourea groups in host design, see: a) E. Fan, S. A. Van Arman, S. Kincaid, A. D. Hamilton, J. Am. Chem. Soc. 1993, 115, 369-370; b) C. S. Wilcox, E. Kim, D. Romano, L. H. Kuo, A. L. Burt, D. P. Curran, Tetrahedron 1995, 51, 621-634; c) S. Nishizawa, P. Bühlmann, M. Iwao, Y. Umezawa, Tetrahedron. Lett. 1995, 36, 6483-6486; d) G. J. Pernía, J. D. Kilburn, J. W. Essex, R. J. Mortirshire-Smith, M. Rowley, J. Am. Chem. Soc. 1996, 118, 10220-10227.
18. For original uses of thiourea groups in host design, see: a) E. Fan, S. A. Van Arman, S. Kincaid, A. D. Hamilton, J. Am. Chem. Soc. 1993, 115, 369-370; b) C. S. Wilcox, E. Kim, D. Romano, L. H. Kuo, A. L. Burt, D. P. Curran, Tetrahedron 1995, 51, 621-634; c) S. Nishizawa, P. Bühlmann, M. Iwao, Y. Umezawa, Tetrahedron. Lett. 1995, 36, 6483-6486; d) G. J. Pernía, J. D. Kilburn, J. W. Essex, R. J. Mortirshire-Smith, M. Rowley, J. Am. Chem. Soc. 1996, 118, 10220-10227.
19. For original uses of thiourea groups in host design, see: a) E. Fan, S. A. Van Arman, S. Kincaid, A. D. Hamilton, J. Am. Chem. Soc. 1993, 115, 369-370; b) C. S. Wilcox, E. Kim, D. Romano, L. H. Kuo, A. L. Burt, D. P. Curran, Tetrahedron 1995, 51, 621-634; c) S. Nishizawa, P. Bühlmann, M. Iwao, Y. Umezawa, Tetrahedron. Lett. 1995, 36, 6483-6486; d) G. J. Pernía, J. D. Kilburn, J. W. Essex, R. J. Mortirshire-Smith, M. Rowley, J. Am. Chem. Soc. 1996, 118, 10220-10227.
20. I. Tvaroska, T. Bleha, Adv. Carbohydr Chem. Biochem. 1989, 47, 45-123.
21. The term cyclotrehalins and the corresponding acronym CTs proposed here for cyclic oligomers of trehalose are in line with the simplified nomenclature proposed for cyclooligosaccharides. See: F. W. Lichtenthaler, S. Immel, Tetrahedron: Asymmetry 1994, 5, 2045-2060.
22. J. L. Jiménez Blanco, J. M. Benito, C. Ortiz Mellet, J. M. García-Fernández, Org. Lett. 1999, 1, 1217-1220.
23. For the original use of this reaction in the preparation of symmetric thioureas, see: J. L. Jiménez Blanco, C. Saitz Barría, J. M. Benito, C. Ortiz Mellet, J. Fuentes, F. Santoyo-González, J. M. García Fernández, Synthesis 1999, 1907-1914.
24. Calculations were performed with the MACROMODEL v6.0 package and the GB/SA continuum solvent model for water. Initially the host molecule was minimized extensively by using the MM2* force field, with the thiourea groups in the Z,Z configuration, the glycosidic torsion angles of the trehalose moieties satisfying the exo-anomeric effect (Φangles H-1-C-1-O-1-C-1′ and H-1′-C-1′-O-1′-C-1 ca. 60°), and the conformation of the lateral chains set to gauche-trans (to angle H-5-C-5-C-6-O-5 ca. 60°), which is consistent with the NMR data. Structures with very similar overall cavity sizes and shapes were obtained when the starting geometry incorporated combinations of Z,Z and Z,E configurations at the thiourea segments.
25. K. A. Connors. Binding Constants. The Measurement of Molecular Complex Stability, Wiley, New York, 1987.
26. 2O. We thank Dr. C. A. Hunter for kindly providing the fitting program.
27. S. Simova, H.-J. Schneider, J. Chem. Soc. Perkin Trans. 2 2000, 1717-1722.