Conformation, Inversion Barrier, and Solvent-Induced Conformational Shift in Exo- and Endo/Exo-Calix[4]arenes

Journal of Organic Chemistry

Volumn 62, Issue 24, 1997, Pages 8350-8360

  Biali, Silvio E ^a   Böhmer, Volker ^b   Brenn, Jörg ^c   Frings, Michael ^b   Thondorf, Iris ^c   Vogt, Walter ^b   Wöhnert, Jens ^c  

^a HEBREW UNIVERSITY OF JERUSALEM   (Israel)

^b JOHANNES GUTENBERG UNIVERSITY   (Germany)

^c MARTIN LUTHER UNIVERSITY HALLE WITTENBERG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000105658     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970967u     Document Type: Article

References (52)

1. For reviews on calixarenes see: (a) Gutsche, C. D. Calixarenes; Royal Society of Chemistry: Cambridge, 1989. (b) Calixarenes: A Versatile Class of Macrocyclic Compounds; Vicens, J., Böhmer, V., Eds.; Kluwer: Dordrecht, 1991. (c) Böhmer, V. Angew. Chem., Int. Ed. Engl. 1995, 34, 713. Gutsche, C. D. Aldrichimica Acta 1995, 25, 1.
2. For reviews on calixarenes see: (a) Gutsche, C. D. Calixarenes; Royal Society of Chemistry: Cambridge, 1989. (b) Calixarenes: A Versatile Class of Macrocyclic Compounds; Vicens, J., Böhmer, V., Eds.; Kluwer: Dordrecht, 1991. (c) Böhmer, V. Angew. Chem., Int. Ed. Engl. 1995, 34, 713. Gutsche, C. D. Aldrichimica Acta 1995, 25, 1.
3. For reviews on calixarenes see: (a) Gutsche, C. D. Calixarenes; Royal Society of Chemistry: Cambridge, 1989. (b) Calixarenes: A Versatile Class of Macrocyclic Compounds; Vicens, J., Böhmer, V., Eds.; Kluwer: Dordrecht, 1991. (c) Böhmer, V. Angew. Chem., Int. Ed. Engl. 1995, 34, 713. Gutsche, C. D. Aldrichimica Acta 1995, 25, 1.
4. For reviews on calixarenes see: (a) Gutsche, C. D. Calixarenes; Royal Society of Chemistry: Cambridge, 1989. (b) Calixarenes: A Versatile Class of Macrocyclic Compounds; Vicens, J., Böhmer, V., Eds.; Kluwer: Dordrecht, 1991. (c) Böhmer, V. Angew. Chem., Int. Ed. Engl. 1995, 34, 713. Gutsche, C. D. Aldrichimica Acta 1995, 25, 1.
5. For a recent review see: Timmerman, P.; Verboom, W.; Reinhoudt, D. N. Tetrahedron 1996, 52, 2663.
6. Böhmer, V.; Dörrenbächer, R.; Frings, M.; Heydenreich, M.; de Paoli, D.; Vogt, W.; Ferguson, G.; Thondorf, I. J. Org. Chem. 1996, 61, 549.
7. (a) Böhmer, V.; Dörrenbächer, R.; Vogt, W.; Zetta, L. Tetrahedron Lett. 1992, 33, 769.
8. (b) Thondorf, I.; Brenn, J.; Brandt, W.; Böhmer, V. Tetrahedron Lett. 1995, 36, 6665.
9. (c) Böhmer, V.; Ferguson, G.; Frings, M. Acta Crystallogr. C 1997, C53, 1293.
10. (a) Sartori, G.; Porta, C.; Bigi, F.; Maggi, R.; Peri, F.; Marzi, E.; Lanfranchi, M.; Pellingheli, M. A. Tetrahedron 1997, 55, 3287.
11. (b) Sorrell, T. N.; Yuan, H. J. Org. Chem. 1997, 62, 1899.
12. Biali, S. E.; Böhmer, V.; Cohen, S.; Ferguson, G.; Grüttner, C.; Grynszpan, F.; Paulus, E. F.; Thondorf, I.; Vogt, W. J. Am. Chem. Soc. 1996, 118, 12938.
13. For other studies of alkanediyl calix[4]arene derivatives see: Sartori, G.; Maggi, R.; Bigi, F.; Arduini, A.; Pastorio, A.; Porta, C. J. Chem. Soc., Perkin Trans. 1 1994, 1657.
14. See for example: Abis, L.; Dalcanale, E.; Du vosel, A.; Spera, S. J. Chem. Soc., Perkin Trans. 2 1990, 2075; Mann, G.; Hennig, I.; Weinelt, F.; Müller, K.; Meusinger, R.; Zahn, G.; Lippmann, T. Supramol. Chem. 1994, 3, 101.
15. See for example: Abis, L.; Dalcanale, E.; Du vosel, A.; Spera, S. J. Chem. Soc., Perkin Trans. 2 1990, 2075; Mann, G.; Hennig, I.; Weinelt, F.; Müller, K.; Meusinger, R.; Zahn, G.; Lippmann, T. Supramol. Chem. 1994, 3, 101.
16. Konishi, H.; Morikawa, O. J. Chem. Soc., Chem. Commun. 1993, 34.
17. Gutsche, C. D.; Bauer, L. J. J. Am. Chem. Soc. 1985, 107, 6052.
18. 10 See: Van Gelder, J. M.; Brenn, J.; Thondorf, I.; Biali, S. E. J. Org. Chem. 1097, 62, 3511.
19. 10 See: Van Gelder, J. M.; Brenn, J.; Thondorf, I.; Biali, S. E. J. Org. Chem. 1097, 62, 3511.
20. Sartori, G.; Bigi, F.; Porta, C.; Maggi, R.; Mora, R. Tetrahedron Lett. 1995, 36, 2311.
21. For identification purposes, the aryl rings of 4 possessing endo or exo hydroxyl groups will be denoted endo- and exo rings, respectively, while the tert-butyl and Me substituted rings of 5a will be dubbed tert-butylphenol and cresol rings.
22. 2 axis. See: Kellie, G. M.; Riddell, F. G. Top. Stereochem. 1974, 8, 225.
23. A preliminary X-ray diffraction study indicates that exo-calixarene 4b also adopts a 1,2-alternate conformation in the crystal.
24. Ugozzoli, F.; Andreetti, G. D. J. Incl. Phenom. 1992, 13, 337.
25. (a) Casiraghi, G.; Cornia, M.; Sartori, G.; Bocchi, V.; Casnati, G.; Andreetti, G. D. Makromol. Chem. 1982, 183, 2611.
26. (b) Casiraghi, G.; Cornia, M.; Ricci, G.; Balduzzi, G.; Casnati, G.; Andreetti, G. D. Makromol. Chem. 1983, 184, 1363.
27. (c) Casiraghi, G.; Cornia, M.; Ricci, G.; Casnati, G.; Andreetti, G. D.; Zetta, L. Macromolecules 1984, 17, 19.
28. (d) Paulus, E.; Böhmer, V. Makromol. Chem. 1984, 185, 1921.
29. See for example: Alfieri, C.; Dradi, E.; Pochini, A.; Ungaro, R. Gazz. Chim. Ital. 1989, 119, 335.
30. A cross-peak between the extrannular aromatic protons of the endo and exo rings which would unambiguously indicate the presence of a cone conformation was not detected.
31. The exchange rate at the coalescence temperature was calculated using the Kurland equation (Kurland, R. J.; Rubin, M. B.; Wise, W. B. J. Chem. Phys. 1964, 40, 2426).
32. Aleksiuk, O.; Grynszpan, F.; Biali, S. E. J. Chem. Soc., Chem. Commun. 1993, 11.
33. The relative orientation of the two pairs of rings could be derived in principle by examining the chemical shifts of the protons of the methylene groups connecting a cresol with a tert-butylphenol ring. In the endo-calixarenes small and large chemical shift differences for the protons of a given methylene group can be taken as an indication of an anti or syn orientation of the neighboring rings, respectively. However, it is unlikely that a similar behavior will be observed for the methylene protons between the tert-butylphenol and the cresol rings, since in the syn and in the anti arrangements both protons are expected to be located in rather similar chemical environments.
34. Anet, F. A. L.; Basus, V. J. J. Magn. Reson. 1978, 32, 339. For Papers using this method see for example: Adams, S. P.; Whitlock, H. W. J. Am. Chem. Soc. 1982, 104, 1602; Casarini, D.; Lunazzi, L.; Macciantelli, D. J. Chem. Soc., Perkin Trans. 2 1985, 1839. For a recent example of the use of this technique for measuring rotational barriers of conformational biased calixarene systems see ref 6.
35. For Papers using this method see for example: Adams, S. P.; Whitlock, H. W. J. Am. Chem. Soc. 1982, 104, 1602;
36. For Papers using this method see for example: Adams, S. P.; Whitlock, H. W. J. Am. Chem. Soc. 1982, 104, 1602; Casarini, D.; Lunazzi, L.; Macciantelli, D. J. Chem. Soc., Perkin Trans. 2 1985, 1839. For a recent example of the use of this technique for measuring rotational barriers of conformational biased calixarene systems see ref 6.
37. Solvent effects affect the conformational stability of substituted resorcarenes. See for example: Shivanuk, A. N.; Pirozhenko, V. V.; Kalchenko, V. I.; Markovsky, L. N. J. Chem. Res. 1995, 374.
38. The partial cone conformation of 5a is chiral, and a dynamic process fast at the NMR time scale and resulting in enantiomerization must be assumed. The observed NOE should correspond to the average of the NOE present in the two enantiomeric conformations.
39. Siegel, J. S.; Anet, F. A. L. J. Org. Chem. 1988, 53, 2629.
40. 6 as a mixture of 1,2- and 1,3-alt conformations.
41. Allinger, N. L.; Yuh, Y. H.; Lii, J.-H. J. Am. Chem. Soc. 1989, 111, 8551. Allinger, N. L.; Rahman, M.; Lii, J.-H. J. Am. Chem. Soc. 1990, 112, 8293.
42. Allinger, N. L.; Yuh, Y. H.; Lii, J.-H. J. Am. Chem. Soc. 1989, 111, 8551. Allinger, N. L.; Rahman, M.; Lii, J.-H. J. Am. Chem. Soc. 1990, 112, 8293.
43. MM3(92) is available from the Quantum Chemistry Program Exchange, University of Indiana, Bloomington, IN 47405.
44. Saunders, M. J. Am. Chem. Soc. 1987, 109, 3150.
45. Thondorf, I.; Brenn, J. J. Mol. Struct. (THEOCHEM) 1997, 398-399, 307.
46. Harada, T.; Ohseto, F.; Shinkai, S. Tetrahedron 1994, 50, 13377.
47. E.g., the cone structure of tris(25,26,27,28-tetrahydroxycalix[4]arene)acetone clathrate (Ungaro, R.; Pochini, A.; Andreetti, G. D.; Sangermano, V. J. Chem. Soc., Perkin Trans. 2 1984, 1979) and the 1,3-alt conformation of 25,27-bis(allyloxy)-26,28-bis(benzoyloxy)calix[4]arene (Georgiev, E. M.; Mague, J. T.; Roundhill, D. M. Supramolecular Chemistry 1993, 2, 53).
48. E.g., the cone structure of tris(25,26,27,28-tetrahydroxycalix[4]arene)acetone clathrate (Ungaro, R.; Pochini, A.; Andreetti, G. D.; Sangermano, V. J. Chem. Soc., Perkin Trans. 2 1984, 1979) and the 1,3-alt conformation of 25,27-bis(allyloxy)-26,28-bis(benzoyloxy)calix[4]arene (Georgiev, E. M.; Mague, J. T.; Roundhill, D. M. Supramolecular Chemistry 1993, 2, 53).
49. ‡ is neglected in the computations.
50. The authors have deposited atomic coordinates for the structures with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK.
51. Zinke, A.; Hanus, F.; Ziegler, E. J. Prakt. Chem 1939, 152, 126.
52. Zinke, A.; Kretz, R.; Leggewie, E.; Hössinger, K. Monatsh. Chem. 1952, 83, 1213.