A conformationally flexible tetrahydroxycalix[4]arene adopting the unusual 1,3-alternate conformation

Journal of Organic Chemistry

Volumn 68, Issue 18, 2003, Pages 7140-7142

  Seri, Noa ^a   Simaan, Samah ^a   Botoshansky, Mark ^b   Kaftory, Menahem ^b   Biali, Silvio E ^a  

^a HEBREW UNIVERSITY OF JERUSALEM   (Israel)

^b TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

CRYSTALS; NUCLEAR MAGNETIC RESONANCE; SPECTROSCOPIC ANALYSIS;

CHIRAL SOLVATING AGENTS;

CONFORMATIONS;

CALIXARENE; TETRAHYDROCALIX[4]ARENE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHIRALITY; CONFORMATION; CRYSTAL STRUCTURE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STRUCTURE ANALYSIS;

EID: 0042839397     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo034874q     Document Type: Article

References (35)

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6. To avoid the steric interaction between m-methyl groups, an octamethyl tetrahydroxycalix[4]arene derivative adopts a flattened cone conformation ("pinched cone" of "boat"). See: Dahan, E.; Biali, S. E. J. Org. Chem, 1991, 56, 7269. A similar distortion of the cone conformation is observed in calix(4]arene derivatives bridged at two para positions at nonvicinal rings. See: Goldmann, H.; Vogt, W.; Paulus, E.; Böhmer, V. J. Am. Chem. Soc. 1988, 110, 6811.
7. To avoid the steric interaction between m-methyl groups, an octamethyl tetrahydroxycalix[4]arene derivative adopts a flattened cone conformation ("pinched cone" of "boat"). See: Dahan, E.; Biali, S. E. J. Org. Chem, 1991, 56, 7269. A similar distortion of the cone conformation is observed in calix(4]arene derivatives bridged at two para positions at nonvicinal rings. See: Goldmann, H.; Vogt, W.; Paulus, E.; Böhmer, V. J. Am. Chem. Soc. 1988, 110, 6811.
8. 13C NMR and FTIR data, it has been concluded that in the two phases the calixarene molecules adopt different conformations (cone and partial cone). See: Shinkai, S.; Nagasaki, T.; Iwamoto, K.; Ikeda, A.; He, G.-X.; Matsuda, T.; Iwamoto, M. Bull. Chem. Soc. Jpn. 1991, 64, 381.
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15. For additional examples of the methylene functionalization of calixarenes, see: (a) Klenke, B.; Näther, C.; Friedrichsen, W. Tetrahedron Lett. 1998, 39, 8967. (b) Middel, O.; Greff, Z.; Taylor, N. J.; Verboom, W.; Reinhoudt, D. N.; Snieckus, V. J. Org. Chem. 2000, 65, 667. (c) Scully, P. A.; Hamilton, T. M.; Bennett, J. L. Org. Lett. 2001, 3, 2741. (d) Agbaria, K.; Biali, S. E. J. Am. Chem. Soc. 2001, 123, 12495. (e) Simaan, S.; Agbaria, K.; Biali, S. E. J. Org. Chem. 2002, 67, 6136. (f) Simaan, S.; Biali, S. E. J. Org. Chem. 2003, 68, 3634.
16. For additional examples of the methylene functionalization of calixarenes, see: (a) Klenke, B.; Näther, C.; Friedrichsen, W. Tetrahedron Lett. 1998, 39, 8967. (b) Middel, O.; Greff, Z.; Taylor, N. J.; Verboom, W.; Reinhoudt, D. N.; Snieckus, V. J. Org. Chem. 2000, 65, 667. (c) Scully, P. A.; Hamilton, T. M.; Bennett, J. L. Org. Lett. 2001, 3, 2741. (d) Agbaria, K.; Biali, S. E. J. Am. Chem. Soc. 2001, 123, 12495. (e) Simaan, S.; Agbaria, K.; Biali, S. E. J. Org. Chem. 2002, 67, 6136. (f) Simaan, S.; Biali, S. E. J. Org. Chem. 2003, 68, 3634.
17. For additional examples of the methylene functionalization of calixarenes, see: (a) Klenke, B.; Näther, C.; Friedrichsen, W. Tetrahedron Lett. 1998, 39, 8967. (b) Middel, O.; Greff, Z.; Taylor, N. J.; Verboom, W.; Reinhoudt, D. N.; Snieckus, V. J. Org. Chem. 2000, 65, 667. (c) Scully, P. A.; Hamilton, T. M.; Bennett, J. L. Org. Lett. 2001, 3, 2741. (d) Agbaria, K.; Biali, S. E. J. Am. Chem. Soc. 2001, 123, 12495. (e) Simaan, S.; Agbaria, K.; Biali, S. E. J. Org. Chem. 2002, 67, 6136. (f) Simaan, S.; Biali, S. E. J. Org. Chem. 2003, 68, 3634.
18. For additional examples of the methylene functionalization of calixarenes, see: (a) Klenke, B.; Näther, C.; Friedrichsen, W. Tetrahedron Lett. 1998, 39, 8967. (b) Middel, O.; Greff, Z.; Taylor, N. J.; Verboom, W.; Reinhoudt, D. N.; Snieckus, V. J. Org. Chem. 2000, 65, 667. (c) Scully, P. A.; Hamilton, T. M.; Bennett, J. L. Org. Lett. 2001, 3, 2741. (d) Agbaria, K.; Biali, S. E. J. Am. Chem. Soc. 2001, 123, 12495. (e) Simaan, S.; Agbaria, K.; Biali, S. E. J. Org. Chem. 2002, 67, 6136. (f) Simaan, S.; Biali, S. E. J. Org. Chem. 2003, 68, 3634.
19. For additional examples of the methylene functionalization of calixarenes, see: (a) Klenke, B.; Näther, C.; Friedrichsen, W. Tetrahedron Lett. 1998, 39, 8967. (b) Middel, O.; Greff, Z.; Taylor, N. J.; Verboom, W.; Reinhoudt, D. N.; Snieckus, V. J. Org. Chem. 2000, 65, 667. (c) Scully, P. A.; Hamilton, T. M.; Bennett, J. L. Org. Lett. 2001, 3, 2741. (d) Agbaria, K.; Biali, S. E. J. Am. Chem. Soc. 2001, 123, 12495. (e) Simaan, S.; Agbaria, K.; Biali, S. E. J. Org. Chem. 2002, 67, 6136. (f) Simaan, S.; Biali, S. E. J. Org. Chem. 2003, 68, 3634.
20. For additional examples of the methylene functionalization of calixarenes, see: (a) Klenke, B.; Näther, C.; Friedrichsen, W. Tetrahedron Lett. 1998, 39, 8967. (b) Middel, O.; Greff, Z.; Taylor, N. J.; Verboom, W.; Reinhoudt, D. N.; Snieckus, V. J. Org. Chem. 2000, 65, 667. (c) Scully, P. A.; Hamilton, T. M.; Bennett, J. L. Org. Lett. 2001, 3, 2741. (d) Agbaria, K.; Biali, S. E. J. Am. Chem. Soc. 2001, 123, 12495. (e) Simaan, S.; Agbaria, K.; Biali, S. E. J. Org. Chem. 2002, 67, 6136. (f) Simaan, S.; Biali, S. E. J. Org. Chem. 2003, 68, 3634.
21. An alternative route for the preparation of methylene-functionalized calixarenes involves the fragment condensation method. See, for example: (a) Tabatai, M.; Vogt, W.; Böhmer, V. Tetrahedron Lett. 1990, 31, 3295. (b) Sartori, G.; Maggi, R.; Bigi, F.; Arduini, A.; Pastorio, A.; Porta, C. J. Chem. Soc., Perkin Trans. 1 1994, 1657. For a review on the synthesis of calixarenes via the stepwise and fragment condensation methods see: Böhmer, V. Liebigs Ann./Recueil 1997, 2019.
22. An alternative route for the preparation of methylene-functionalized calixarenes involves the fragment condensation method. See, for example: (a) Tabatai, M.; Vogt, W.; Böhmer, V. Tetrahedron Lett. 1990, 31, 3295. (b) Sartori, G.; Maggi, R.; Bigi, F.; Arduini, A.; Pastorio, A.; Porta, C. J. Chem. Soc., Perkin Trans. 1 1994, 1657. For a review on the synthesis of calixarenes via the stepwise and fragment condensation methods see: Böhmer, V. Liebigs Ann./Recueil 1997, 2019.
23. An alternative route for the preparation of methylene-functionalized calixarenes involves the fragment condensation method. See, for example: (a) Tabatai, M.; Vogt, W.; Böhmer, V. Tetrahedron Lett. 1990, 31, 3295. (b) Sartori, G.; Maggi, R.; Bigi, F.; Arduini, A.; Pastorio, A.; Porta, C. J. Chem. Soc., Perkin Trans. 1 1994, 1657. For a review on the synthesis of calixarenes via the stepwise and fragment condensation methods see: Böhmer, V. Liebigs Ann./Recueil 1997, 2019.
24. Gutsche, C. D.; Dhawan, B.; Levine, J. A.; No, K. H.; Bauer, L. J. Tetrahedron 1983, 39, 403.
25. The crystal structure of the partial cone form of 2 has been reported. See: Rizzoli, C.; Andreetti, G. D.; Ungaro, R.; Pochini, A. J. Mol. Struct. 1982, 82, 133.
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28. For a recent example of the use of a CSA for following the exchange of enantiotopic groups, see: Grilli, S.; Lunazzi, L.; Mazzanti, A.; Casarini, D.; Femoni, C. J. Org. Chem. 2001, 66, 488. (b) For an example of the use of a chiral auxiliary for the determination of the rotational barrier of a calixarene adopting the 1,3-alternate conformation, see: Parzuchowski, P.; Böhmer, V.; Biali, S. E.; Thondorf, I. Tetrahedron: Asymmetry 2000, 11, 2393.
29. For a recent example of the use of a CSA for following the exchange of enantiotopic groups, see: Grilli, S.; Lunazzi, L.; Mazzanti, A.; Casarini, D.; Femoni, C. J. Org. Chem. 2001, 66, 488. (b) For an example of the use of a chiral auxiliary for the determination of the rotational barrier of a calixarene adopting the 1,3-alternate conformation, see: Parzuchowski, P.; Böhmer, V.; Biali, S. E.; Thondorf, I. Tetrahedron: Asymmetry 2000, 11, 2393.
30. The NMR sample was prepared by dissolving 190 mg of the CSA and 1.5 mg 3 (a 507:1 molar equivalent ratio) in ca. 0.5 mL of solvent.
31. gNMR v4.1.0. Cherwell Scientific Publishing: Oxford, UK.
32. Gutsche, C. D.; Bauer, L. J. J. Am. Chem. Soc. 1985, 107, 6052.
33. 1, a = b = 20.437(4), c = 16.810(3) A, Z = 4. The solvent molecules were disordered and were refined using a rigid group treatment.
34. For a review on calculations of the conformation of calixarenes see: Thondorf, I. In Calixarenes 2001; Asfari, Z., Böhmer, V., Harrowfield, J., Vicens, J., Eds.; Kluwer Academic Publishers: Dordrecht, 2001; p 280.
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