Alkanediyl bridged calix[4]arenes: Synthesis, conformational analysis, and rotational barriers

Journal of the American Chemical Society

Volumn 118, Issue 51, 1996, Pages 12938-12949

  Biali, Silvio E ^a   Böhmer, Volker ^b   Cohen, Shmuel ^a   Ferguson, George ^c   Grüttner, Cordula ^b   Grynszpan, Flavio ^a   Paulus, Erich F ^d   Thondorf, Iris ^e   Vogt, Walter ^b  

^a HEBREW UNIVERSITY OF JERUSALEM   (Israel)

^b JOHANNES GUTENBERG UNIVERSITY   (Germany)

^c UNIVERSITY OF GUELPH   (Canada)

^d SANOFI   (France)

^e MARTIN LUTHER UNIVERSITY HALLE WITTENBERG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

CALIXARENE;

ARTICLE; DRUG STRUCTURE; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; X RAY ANALYSIS;

EID: 0030450615     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960883n     Document Type: Article

References (55)

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2. For optimized procedures see: Gutsche, C. D.: Iqbal, M. Org. Synth. 1990, 68, 234-237. Stewart, D. R.; Gutsche, C. D. Org. Prep. Proc. Int. 1993, 25, 137-139. Gutsche, C. D.; Dhawan, B.; Leonis, M.; Stewart. D. Org. Synth. 1990, 68. 238-242. Munch, J. H.: Gutsche, C. D. Org. Synth. 1990, 68, 243-246.
3. For optimized procedures see: Gutsche, C. D.: Iqbal, M. Org. Synth. 1990, 68, 234-237. Stewart, D. R.; Gutsche, C. D. Org. Prep. Proc. Int. 1993, 25, 137-139. Gutsche, C. D.; Dhawan, B.; Leonis, M.; Stewart. D. Org. Synth. 1990, 68. 238-242. Munch, J. H.: Gutsche, C. D. Org. Synth. 1990, 68, 243-246.
4. For optimized procedures see: Gutsche, C. D.: Iqbal, M. Org. Synth. 1990, 68, 234-237. Stewart, D. R.; Gutsche, C. D. Org. Prep. Proc. Int. 1993, 25, 137-139. Gutsche, C. D.; Dhawan, B.; Leonis, M.; Stewart. D. Org. Synth. 1990, 68. 238-242. Munch, J. H.: Gutsche, C. D. Org. Synth. 1990, 68, 243-246.
5. For a recent review on calixarenes, see: Böhmer, V. Angew. Chem., Int. Ed. Engl. 1995, 34, 713-745, and references cited there.
6. For an early review, see: van Loon, J. D.; Verboom, W.; Reinhoudt, D. N. Org. Prep. Proc. Int. 1992, 24, 437-462.
7. Janssen, R. G.; Verboom, W.; Harkema, S.; van Hummel, G. J.; Reinhoudt, D. N.; Pochini, A.; Ungaro, R.; Prados, P.; de Mendoza, J. J. Chem. Soc., Chem. Comm. 1993, 506-508. Janssen, R. G.; Verboom, W.; Reinhoudt, D. N.; Casnati, A.; Freriks, M.; Pochini, A.; Uggozoli, F.; Ungaro, R.; Nieto, P. M.; Carramolino, M.; Cuevas, F.; Prados, P.; de Mendoza, J. Synthesis 1993, 380-386. de Mendoza, J.; Carramolino, M.; Cuevas, F.; Nieto, P. M.; Prados, P.; Reinhoudt, D. N.; Verboom, W.; Ungaro, R.; Casnati, A. Synthesis 1994, 47-50. Casnati, A.: Minari, P.; Pochini, A.; Ungaro, R. J. Chem. Soc., Chem. Commun. 1991, 1413-1414. Rogers, J. S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3152-3159. Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166.
8. Janssen, R. G.; Verboom, W.; Harkema, S.; van Hummel, G. J.; Reinhoudt, D. N.; Pochini, A.; Ungaro, R.; Prados, P.; de Mendoza, J. J. Chem. Soc., Chem. Comm. 1993, 506-508. Janssen, R. G.; Verboom, W.; Reinhoudt, D. N.; Casnati, A.; Freriks, M.; Pochini, A.; Uggozoli, F.; Ungaro, R.; Nieto, P. M.; Carramolino, M.; Cuevas, F.; Prados, P.; de Mendoza, J. Synthesis 1993, 380-386. de Mendoza, J.; Carramolino, M.; Cuevas, F.; Nieto, P. M.; Prados, P.; Reinhoudt, D. N.; Verboom, W.; Ungaro, R.; Casnati, A. Synthesis 1994, 47-50. Casnati, A.: Minari, P.; Pochini, A.; Ungaro, R. J. Chem. Soc., Chem. Commun. 1991, 1413-1414. Rogers, J. S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3152-3159. Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166.
9. Janssen, R. G.; Verboom, W.; Harkema, S.; van Hummel, G. J.; Reinhoudt, D. N.; Pochini, A.; Ungaro, R.; Prados, P.; de Mendoza, J. J. Chem. Soc., Chem. Comm. 1993, 506-508. Janssen, R. G.; Verboom, W.; Reinhoudt, D. N.; Casnati, A.; Freriks, M.; Pochini, A.; Uggozoli, F.; Ungaro, R.; Nieto, P. M.; Carramolino, M.; Cuevas, F.; Prados, P.; de Mendoza, J. Synthesis 1993, 380-386. de Mendoza, J.; Carramolino, M.; Cuevas, F.; Nieto, P. M.; Prados, P.; Reinhoudt, D. N.; Verboom, W.; Ungaro, R.; Casnati, A. Synthesis 1994, 47-50. Casnati, A.: Minari, P.; Pochini, A.; Ungaro, R. J. Chem. Soc., Chem. Commun. 1991, 1413-1414. Rogers, J. S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3152-3159. Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166.
10. Janssen, R. G.; Verboom, W.; Harkema, S.; van Hummel, G. J.; Reinhoudt, D. N.; Pochini, A.; Ungaro, R.; Prados, P.; de Mendoza, J. J. Chem. Soc., Chem. Comm. 1993, 506-508. Janssen, R. G.; Verboom, W.; Reinhoudt, D. N.; Casnati, A.; Freriks, M.; Pochini, A.; Uggozoli, F.; Ungaro, R.; Nieto, P. M.; Carramolino, M.; Cuevas, F.; Prados, P.; de Mendoza, J. Synthesis 1993, 380-386. de Mendoza, J.; Carramolino, M.; Cuevas, F.; Nieto, P. M.; Prados, P.; Reinhoudt, D. N.; Verboom, W.; Ungaro, R.; Casnati, A. Synthesis 1994, 47-50. Casnati, A.: Minari, P.; Pochini, A.; Ungaro, R. J. Chem. Soc., Chem. Commun. 1991, 1413-1414. Rogers, J. S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3152-3159. Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166.
11. Janssen, R. G.; Verboom, W.; Harkema, S.; van Hummel, G. J.; Reinhoudt, D. N.; Pochini, A.; Ungaro, R.; Prados, P.; de Mendoza, J. J. Chem. Soc., Chem. Comm. 1993, 506-508. Janssen, R. G.; Verboom, W.; Reinhoudt, D. N.; Casnati, A.; Freriks, M.; Pochini, A.; Uggozoli, F.; Ungaro, R.; Nieto, P. M.; Carramolino, M.; Cuevas, F.; Prados, P.; de Mendoza, J. Synthesis 1993, 380-386. de Mendoza, J.; Carramolino, M.; Cuevas, F.; Nieto, P. M.; Prados, P.; Reinhoudt, D. N.; Verboom, W.; Ungaro, R.; Casnati, A. Synthesis 1994, 47-50. Casnati, A.: Minari, P.; Pochini, A.; Ungaro, R. J. Chem. Soc., Chem. Commun. 1991, 1413-1414. Rogers, J. S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3152-3159. Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166.
12. Janssen, R. G.; Verboom, W.; Harkema, S.; van Hummel, G. J.; Reinhoudt, D. N.; Pochini, A.; Ungaro, R.; Prados, P.; de Mendoza, J. J. Chem. Soc., Chem. Comm. 1993, 506-508. Janssen, R. G.; Verboom, W.; Reinhoudt, D. N.; Casnati, A.; Freriks, M.; Pochini, A.; Uggozoli, F.; Ungaro, R.; Nieto, P. M.; Carramolino, M.; Cuevas, F.; Prados, P.; de Mendoza, J. Synthesis 1993, 380-386. de Mendoza, J.; Carramolino, M.; Cuevas, F.; Nieto, P. M.; Prados, P.; Reinhoudt, D. N.; Verboom, W.; Ungaro, R.; Casnati, A. Synthesis 1994, 47-50. Casnati, A.: Minari, P.; Pochini, A.; Ungaro, R. J. Chem. Soc., Chem. Commun. 1991, 1413-1414. Rogers, J. S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3152-3159. Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166.
13. Stewart, D. R.; Krawiec, M.: Kashyap, R. P.; Watson, W. H.; Gutsche, C. D. J. Am. Chem. Soc. 1995, 117, 586-601.
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15. Neri, P.; Geraci, C.; Piattelli, M. Tetrahedron Lett. 1993, 34, 3319-3322. Neri, P.; Battocolo, E.; Cunsolo. F.; Geraci, C.; Piattelli, M. J. Org. Chem. 1994, 59, 3880-3889. Cunsolo, F.; Piattelli, M.; Neri, P. J. Chem. Soc., Chem. Commun. 1994, 1917-1918. Cunsolo, F.; Consoli, G. M. L.; Piattelli, M.; Neri, P. Tetrahedron Lett. 1995, 36, 3751-3754. Geraci, C.; Piattelli, M.; Neri, P. Tetrahedron Lett. 1995, 36, 5429-5432. Neri, P.; Geraci, C.; Piattelli, M. J. Org. Chem. 1995, 60, 4126-4135.
16. Neri, P.; Geraci, C.; Piattelli, M. Tetrahedron Lett. 1993, 34, 3319-3322. Neri, P.; Battocolo, E.; Cunsolo. F.; Geraci, C.; Piattelli, M. J. Org. Chem. 1994, 59, 3880-3889. Cunsolo, F.; Piattelli, M.; Neri, P. J. Chem. Soc., Chem. Commun. 1994, 1917-1918. Cunsolo, F.; Consoli, G. M. L.; Piattelli, M.; Neri, P. Tetrahedron Lett. 1995, 36, 3751-3754. Geraci, C.; Piattelli, M.; Neri, P. Tetrahedron Lett. 1995, 36, 5429-5432. Neri, P.; Geraci, C.; Piattelli, M. J. Org. Chem. 1995, 60, 4126-4135.
17. Neri, P.; Geraci, C.; Piattelli, M. Tetrahedron Lett. 1993, 34, 3319-3322. Neri, P.; Battocolo, E.; Cunsolo. F.; Geraci, C.; Piattelli, M. J. Org. Chem. 1994, 59, 3880-3889. Cunsolo, F.; Piattelli, M.; Neri, P. J. Chem. Soc., Chem. Commun. 1994, 1917-1918. Cunsolo, F.; Consoli, G. M. L.; Piattelli, M.; Neri, P. Tetrahedron Lett. 1995, 36, 3751-3754. Geraci, C.; Piattelli, M.; Neri, P. Tetrahedron Lett. 1995, 36, 5429-5432. Neri, P.; Geraci, C.; Piattelli, M. J. Org. Chem. 1995, 60, 4126-4135.
18. Neri, P.; Geraci, C.; Piattelli, M. Tetrahedron Lett. 1993, 34, 3319-3322. Neri, P.; Battocolo, E.; Cunsolo. F.; Geraci, C.; Piattelli, M. J. Org. Chem. 1994, 59, 3880-3889. Cunsolo, F.; Piattelli, M.; Neri, P. J. Chem. Soc., Chem. Commun. 1994, 1917-1918. Cunsolo, F.; Consoli, G. M. L.; Piattelli, M.; Neri, P. Tetrahedron Lett. 1995, 36, 3751-3754. Geraci, C.; Piattelli, M.; Neri, P. Tetrahedron Lett. 1995, 36, 5429-5432. Neri, P.; Geraci, C.; Piattelli, M. J. Org. Chem. 1995, 60, 4126-4135.
19. Neri, P.; Geraci, C.; Piattelli, M. Tetrahedron Lett. 1993, 34, 3319-3322. Neri, P.; Battocolo, E.; Cunsolo. F.; Geraci, C.; Piattelli, M. J. Org. Chem. 1994, 59, 3880-3889. Cunsolo, F.; Piattelli, M.; Neri, P. J. Chem. Soc., Chem. Commun. 1994, 1917-1918. Cunsolo, F.; Consoli, G. M. L.; Piattelli, M.; Neri, P. Tetrahedron Lett. 1995, 36, 3751-3754. Geraci, C.; Piattelli, M.; Neri, P. Tetrahedron Lett. 1995, 36, 5429-5432. Neri, P.; Geraci, C.; Piattelli, M. J. Org. Chem. 1995, 60, 4126-4135.
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21. Sartori, G.; Maggi, R.; Bigi, F.; Arduini, A.; Pastorio, A.; Porta, C. J. Chem. Soc., Perkin Trans. 1 1994, 1657-1658; see, also ref. 22.
22. 2 and/or different substituents in p-position.
23. For a preliminary report, see: Griittner, C.; Böhmer, V.; Vogt, W.; Thondorf, I.; Biali, S. E.; Grynszpan, F. Tetrahedron Lett. 1994, 35, 6267-6270.
24. Böhmer, V.; Merkel, L.; Kunz, U. J. Chem. Soc., Chem. Commun. 1987, 896-897.
25. Grüttner, C.; Böhmer, V.; Assmus, R.; Scherf, S. J. Chem. Soc., Perkin Trans. 1 1995, 93-94.
26. See, for example: Böhmer, V.; Dörrenbächer, R.; Vogt, W.; Zetta, L. Tetrahedron Lett. 1992, 33, 769-772. Zetta, L.; Wolff, A. Vogt, W.; Platt, K.-L.; Böhmer, V. Tetrahedron 1991, 47, 1911-1924. Alfieri, C.; Dradi, E.; Pochini, A.; Ungaro, R. Gazz. Chim. Ital. 1989, 119, 335-338
27. See, for example: Böhmer, V.; Dörrenbächer, R.; Vogt, W.; Zetta, L. Tetrahedron Lett. 1992, 33, 769-772. Zetta, L.; Wolff, A. Vogt, W.; Platt, K.-L.; Böhmer, V. Tetrahedron 1991, 47, 1911-1924. Alfieri, C.; Dradi, E.; Pochini, A.; Ungaro, R. Gazz. Chim. Ital. 1989, 119, 335-338
28. See, for example: Böhmer, V.; Dörrenbächer, R.; Vogt, W.; Zetta, L. Tetrahedron Lett. 1992, 33, 769-772. Zetta, L.; Wolff, A. Vogt, W.; Platt, K.-L.; Böhmer, V. Tetrahedron 1991, 47, 1911-1924. Alfieri, C.; Dradi, E.; Pochini, A.; Ungaro, R. Gazz. Chim. Ital. 1989, 119, 335-338
29. Günther, H. NMR Spectroscopy; Wiley: Chichester, 1980: p 86.
30. See, for example: Eliel, E. L.: Wilen, S. H. Stereochemistry of Organic Compound; Wiley: New York. 1994; p 693.
31. Anet, F. A. L.; Basus, V. J. J. Mag. Res. 1978, 32, 339-343. For papers using this method see, for example: Adams, S. P.; Whitlock, H. W. J. Am. Chem. Soc. 1982, 104, 1602-1611. Casarini, D.; Lunazzi, L.; Macciantelli, D. J. Chem. Soc., Perkin Trans. 2 1985, 1839-1844.
32. Anet, F. A. L.; Basus, V. J. J. Mag. Res. 1978, 32, 339-343. For papers using this method see, for example: Adams, S. P.; Whitlock, H. W. J. Am. Chem. Soc. 1982, 104, 1602-1611. Casarini, D.; Lunazzi, L.; Macciantelli, D. J. Chem. Soc., Perkin Trans. 2 1985, 1839-1844.
33. Anet, F. A. L.; Basus, V. J. J. Mag. Res. 1978, 32, 339-343. For papers using this method see, for example: Adams, S. P.; Whitlock, H. W. J. Am. Chem. Soc. 1982, 104, 1602-1611. Casarini, D.; Lunazzi, L.; Macciantelli, D. J. Chem. Soc., Perkin Trans. 2 1985, 1839-1844.
34. For a recent compilation of "A" values see ref. 15, p 697.
35. Gutsche, C. D.; Bauer, L. J. J. Am. Chem. Soc. 1985, 107, 6052-6059.
36. Pairs of signals related by COSY belong to the same diastereomer (otherwise they will not be mutually coupled) and cannot mutually exchange by the diastereomerization process.
37. C) at the coalescence temperatures were calculated by either the Gutowsky-Holm's (Gutowsky, H. S.; Holm, C. H. J. Chem. Phys. 1956, 25, 1228-1234) or Kurland's equations (Kurland, R. J.; Rubin, M. B.; Wise, W. B. J. Chem. Phys. 1964, 40, 2426-2427).
38. C) at the coalescence temperatures were calculated by either the Gutowsky-Holm's (Gutowsky, H. S.; Holm, C. H. J. Chem. Phys. 1956, 25, 1228-1234) or Kurland's equations (Kurland, R. J.; Rubin, M. B.; Wise, W. B. J. Chem. Phys. 1964, 40, 2426-2427).
39. The chemical shifts under fast exchange conditions are 3.90 and 3.88 ppm (J = 13.9 Hz) for the methylene groups adjacent to the alkanediyl group, and 3.89 and 3.85 ppm (J = 13.6 Hz) for the distal methylene groups.
40. 1H NMR studies for two bishomooxacalix-[4]arenes substituted by phenyl at two opposite methylene bridges were recently reported by Sartori, G.; Bigi, F.; Porta, C.; Maggi, R.; Peri, F. Tetrahedron Lett. 1995, 35, 8323-8326
41. The examination of strongly biased systems by integration of the NMR signals is difficult, since the peak(s) of the minor conformer must be both detected and positively identified. In the case of 5f and 5e, no signal corresponding to the axial conformer could be detected in pyridine. In these cases the reported value is an estimation of the lower limit of the equilibrium constant. The small signal of the methine proton of the axial conformer of 5h (at 5.79 ppm) was identified by a NOESY spectrum which displayed a magnetization transfer cross peak between this signal and the methine proton of the major (axial) conformer at 7.35 ppm.
42. 2O obtained from pyridine also showed the molecule in the bis-equatorial conformation. The structure could not be sufficiently refined, however.
43. For a similar intercalation-type bilayer arrangement, see: Goldberg, I. J. Incl. Phenom. 1984, 1, 349-364; compare also Davies, J. E. D. J. Mol. Struct. 1981, 75, 1-12. For layered structures of calixarenes, see: Atwood. J. L., Bott, S. L. in Calixarenes, A Versatile Class of Macrocyclic Compounds; Vicens, J., Böhmer, V., Eds.; Kluwer: 1991.
44. For a similar intercalation-type bilayer arrangement, see: Goldberg, I. J. Incl. Phenom. 1984, 1, 349-364; compare also Davies, J. E. D. J. Mol. Struct. 1981, 75, 1-12. For layered structures of calixarenes, see: Atwood. J. L., Bott, S. L. in Calixarenes, A Versatile Class of Macrocyclic Compounds; Vicens, J., Böhmer, V., Eds.; Kluwer: 1991.
45. For a similar intercalation-type bilayer arrangement, see: Goldberg, I. J. Incl. Phenom. 1984, 1, 349-364; compare also Davies, J. E. D. J. Mol. Struct. 1981, 75, 1-12. For layered structures of calixarenes, see: Atwood. J. L., Bott, S. L. in Calixarenes, A Versatile Class of Macrocyclic Compounds; Vicens, J., Böhmer, V., Eds.; Kluwer: 1991.
46. Acetonitrile is often found in the cavity of calix[4]arenes or calix-[4]arene derivatives, but usually favoring fourfold symmetry. For an early example see: McKervey, M. A., Seward, E. M., Ferguson, G.; Ruhl, B. L. J. Org. Chem. 1986, 51, 3581-3584; for a very recent one: Böhmer, V.; Dörrenbächer, R.; Frings, M.; Heydenreich, M.; de Paoli, D.; Vogt, W.; Ferguson, G.; Thondorf, I. J. Org. Chem. 1996, 61, 549-559.
47. Acetonitrile is often found in the cavity of calix[4]arenes or calix-[4]arene derivatives, but usually favoring fourfold symmetry. For an early example see: McKervey, M. A., Seward, E. M., Ferguson, G.; Ruhl, B. L. J. Org. Chem. 1986, 51, 3581-3584; for a very recent one: Böhmer, V.; Dörrenbächer, R.; Frings, M.; Heydenreich, M.; de Paoli, D.; Vogt, W.; Ferguson, G.; Thondorf, I. J. Org. Chem. 1996, 61, 549-559.
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