Totally and partially saturated calixarene analogues

Journal of the American Chemical Society

Volumn 120, Issue 13, 1998, Pages 3060-3067

  Columbus, Ishay ^a   Biali, Silvio E ^a  

^a HEBREW UNIVERSITY OF JERUSALEM   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

CALIXARENE; CYCLODEXTRIN DERIVATIVE; CYCLOHEXANOL;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; HYDROGENATION; ISOMERISM; MOLECULAR DYNAMICS; SYNTHESIS;

EID: 0032495763     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja974097+     Document Type: Article

References (43)

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2. For recent reviews on the conformation of cyclohexyl rings, see: (a) Conformational Behavior of Six Membered Rings; Juaristi, E., Ed.; VCH Publishers: New York, 1995. (b) Mann, G. Z. Chem. 1990, 30, 1. (c) Anderson, J. E. In The Chemistry of Alkanes and Cycloalkanes; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, 1992, Chapter 3. (d) Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; Wiley: New York, 1994.
3. For recent reviews on the conformation of cyclohexyl rings, see: (a) Conformational Behavior of Six Membered Rings; Juaristi, E., Ed.; VCH Publishers: New York, 1995. (b) Mann, G. Z. Chem. 1990, 30, 1. (c) Anderson, J. E. In The Chemistry of Alkanes and Cycloalkanes; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, 1992, Chapter 3. (d) Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; Wiley: New York, 1994.
4. For recent reviews on the conformation of cyclohexyl rings, see: (a) Conformational Behavior of Six Membered Rings; Juaristi, E., Ed.; VCH Publishers: New York, 1995. (b) Mann, G. Z. Chem. 1990, 30, 1. (c) Anderson, J. E. In The Chemistry of Alkanes and Cycloalkanes; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, 1992, Chapter 3. (d) Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; Wiley: New York, 1994.
5. For recent reviews on the conformation of cyclohexyl rings, see: (a) Conformational Behavior of Six Membered Rings; Juaristi, E., Ed.; VCH Publishers: New York, 1995. (b) Mann, G. Z. Chem. 1990, 30, 1. (c) Anderson, J. E. In The Chemistry of Alkanes and Cycloalkanes; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, 1992, Chapter 3. (d) Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; Wiley: New York, 1994.
6. For a recent example of a paracyclophane incorporating a cyclohexyl ring, see: Yang, F.-M.; Lin, S.-T. J. Org. Chem. 1997, 62, 2727.
7. 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. (d) Gutsche, C. D. Aldrichimica Acta 1995, 28, 1.
8. 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. (d) Gutsche, C. D. Aldrichimica Acta 1995, 28, 1.
9. 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. (d) Gutsche, C. D. Aldrichimica Acta 1995, 28, 1.
10. 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. (d) Gutsche, C. D. Aldrichimica Acta 1995, 28, 1.
11. Grynszpan, F.; Biali, S. E. Chem. Commun. 1996, 195.
12. For example, see: Columbus, I.; Hoffman, R. E.; Biali, S. E. J. Am. Chem. Soc. 1996. 118, 6890.
13. (a) Bilyk, A.; Harrowfield, J. M.; Skelton, B. W.; White, A. H. An. Quim. Int. Ed. 1997, 93, 363.
14. (b) Bilyk, A.; Harrowfield, J. M.; Skelton, B. W.; White, A. H. J. Chem. Soc., Dalton Trans. 1997, 4251.
15. Azran, J.; Buchman, O.; Amer, I.; Blum, J. J. Mol. Catal. 1986, 34, 229.
16. Because the alcohol carbon in 6a and 6d qualifies as a pseudoasymmetric center (i.e., a stereogenic nonchirotopic atom), its configuration is described with a lowercase letter (Cahn, R. S.; Ingold, C.; Prelog, V. Angew. Chem., Int. Ed. Eng. 1966, 6, 385). See also: Mislow, K.; Siegel, J. J. Am. Chem. Soc. 1984, 106, 6, 3319.
17. Because the alcohol carbon in 6a and 6d qualifies as a pseudoasymmetric center (i.e., a stereogenic nonchirotopic atom), its configuration is described with a lowercase letter (Cahn, R. S.; Ingold, C.; Prelog, V. Angew. Chem., Int. Ed. Eng. 1966, 6, 385). See also: Mislow, K.; Siegel, J. J. Am. Chem. Soc. 1984, 106, 6, 3319.
18. For exceptions to these rules, see: (a) Golan, O.; Goren, Z.; Biali, S. E. J. Am. Chem. Soc. 1990, 112, 9300. (b) Biali, S. E. J. Org. Chem. 1992, 57, 2979. (c) Kang, F.-A.; Yin, C.-L. J. Am. Chem. Soc. 1997, 119, 8562. (d) Weiser, J.; Golan, O.; Fitjer, L.; Biali, S. E. J. Org. Chem. 1996, 61, 8277. (e) ref 6.
19. For exceptions to these rules, see: (a) Golan, O.; Goren, Z.; Biali, S. E. J. Am. Chem. Soc. 1990, 112, 9300. (b) Biali, S. E. J. Org. Chem. 1992, 57, 2979. (c) Kang, F.-A.; Yin, C.-L. J. Am. Chem. Soc. 1997, 119, 8562. (d) Weiser, J.; Golan, O.; Fitjer, L.; Biali, S. E. J. Org. Chem. 1996, 61, 8277. (e) ref 6.
20. For exceptions to these rules, see: (a) Golan, O.; Goren, Z.; Biali, S. E. J. Am. Chem. Soc. 1990, 112, 9300. (b) Biali, S. E. J. Org. Chem. 1992, 57, 2979. (c) Kang, F.-A.; Yin, C.-L. J. Am. Chem. Soc. 1997, 119, 8562. (d) Weiser, J.; Golan, O.; Fitjer, L.; Biali, S. E. J. Org. Chem. 1996, 61, 8277. (e) ref 6.
21. For exceptions to these rules, see: (a) Golan, O.; Goren, Z.; Biali, S. E. J. Am. Chem. Soc. 1990, 112, 9300. (b) Biali, S. E. J. Org. Chem. 1992, 57, 2979. (c) Kang, F.-A.; Yin, C.-L. J. Am. Chem. Soc. 1997, 119, 8562. (d) Weiser, J.; Golan, O.; Fitjer, L.; Biali, S. E. J. Org. Chem. 1996, 61, 8277. (e) ref 6.
22. For exceptions to these rules, see: (a) Golan, O.; Goren, Z.; Biali, S. E. J. Am. Chem. Soc. 1990, 112, 9300. (b) Biali, S. E. J. Org. Chem. 1992, 57, 2979. (c) Kang, F.-A.; Yin, C.-L. J. Am. Chem. Soc. 1997, 119, 8562. (d) Weiser, J.; Golan, O.; Fitjer, L.; Biali, S. E. J. Org. Chem. 1996, 61, 8277. (e) ref 6.
23. β") are oriented gauche/gauche or anti/gauche to the pair of bridging methylene protons, respectively.
24. Allinger, N. L. MM3 1994 Force Field for UNIX and VAX (updated June 3, 1994).
25. This is further supported by MM3 calculations on analogues of 6a and 6d in which the cyclohexanol OH was replaced by a methyl. Although the methyl substituent is not involved in hydrogen bonds, the isomer with the axial methyl is the lower energy form.
26. Willem, R.; Pepermans, H.; Hoogzand, C.; Hallenga, K.; Gielen, M. J. Am. Chem. Soc. 1981, 103, 2297. See also: Biali, S. E.; Buda, A. B.; Mislow, K. J. Org. Chem. 1988, 53, 1289.
27. Willem, R.; Pepermans, H.; Hoogzand, C.; Hallenga, K.; Gielen, M. J. Am. Chem. Soc. 1981, 103, 2297. See also: Biali, S. E.; Buda, A. B.; Mislow, K. J. Org. Chem. 1988, 53, 1289.
28. The symmetry number is the number of indistinguishable but nonidentical positions in which the molecule can be turned by rigid rotation. See ref 2d, p 96.
29. The number of symmetry matrixes is inversely proportional to the symmetry number. See: Brocas, J.; Gielen, M.; Willem, R. The Permutational Approach to Dynamic Stereochemistry, McGraw-Hill, New York, 1983, Chapter 8.
30. Günther, H. NMR Spectroscopy; Wiley: Chichester, 1980: p 72.
31. In endocalixarenes the axial protons of the bridging methylenes resonate at a lower field than the equatorial protons (Alfieri, C.; Dradi, E.; Pochini, A.; Ungaro, R. Gazz. Chim. Ital. 1989, 119, 335). However, in exocalixarenes this behavior is reverted. See: Biali, S. E.; Böhmer, V.; Brenn, J.; Frings, M.; Thondorf, I.; Vogt, W.; Wöhnert, J. J. Org. Chem. 1997, 104, 5163.
32. In endocalixarenes the axial protons of the bridging methylenes resonate at a lower field than the equatorial protons (Alfieri, C.; Dradi, E.; Pochini, A.; Ungaro, R. Gazz. Chim. Ital. 1989, 119, 335). However, in exocalixarenes this behavior is reverted. See: Biali, S. E.; Böhmer, V.; Brenn, J.; Frings, M.; Thondorf, I.; Vogt, W.; Wöhnert, J. J. Org. Chem. 1997, 104, 5163.
33. Steric crowding increases the RCR bond angle in disubstituted methanes. For example, according to X-ray crystallography this angle is 129.3° in ditriptycyl methane (Johnson, C. A.; Guenzi, A.; Nachbar, R. B.; Jr.; Blount, J. F.; Wennerström, O.; Mislow, K. J. Am. Chem. Soc. 1982, 104, 5163).
34. β carbons.
35. McMurry, J. E.; Phelan, J. C. Tetrahedron Lett. 1991, 32, 5655.
36. The symmetries considered correspond to the "averaged symmetries", i.e., the (nonrigid) symmetries which result when all conformational interconversions are fast. The symmetry of the preferred conformation of a given isomer may be identical to or lower than the averaged symmetry.
37. Donaldson, J. D.; Ross, S. D. Symmetry and Stereochemistry; Wiley: New York, 1972.
38. 2.
39. Krassig, H. Makromol. Chem. 1956, 17, 77. See also Dale, J.; Romming, C.; Suissa, M. R. J. Chem. Soc., Chem. Commun. 1995, 1631; Suissa, M. R.; Romming, C.; Dale. J. Chem. Commun. 1997, 113.
40. Krassig, H. Makromol. Chem. 1956, 17, 77. See also Dale, J.; Romming, C.; Suissa, M. R. J. Chem. Soc., Chem. Commun. 1995, 1631; Suissa, M. R.; Romming, C.; Dale. J. Chem. Commun. 1997, 113.
41. Krassig, H. Makromol. Chem. 1956, 17, 77. See also Dale, J.; Romming, C.; Suissa, M. R. J. Chem. Soc., Chem. Commun. 1995, 1631; Suissa, M. R.; Romming, C.; Dale. J. Chem. Commun. 1997, 113.
42. Murray-Rust, P. Acta Crystallogr., Sect. B 1975, 31, 583.
43. Dale, J.; Romming, C.; Sigvartsen, T. Acta Chem. Scand. 1991, 45, 1071.