A fast access to non-symmetrically substituted 1,3-alternate conformers of calix[4]arenes

European Journal of Organic Chemistry

Volumn , Issue 13, 2004, Pages 2848-2852

  Kleij, Arjan W ^a,c   Prados, Pilar ^a   De Mendoza, Javier ^a,b  

^a UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

^b INSTITUTE OF CHEMICAL RESEARCH OF CATALONIA ICIQ   (Spain)

^c UNIVERSITY OF AMSTERDAM   (Netherlands)

Author keywords

Alkylation; Building blocks; Calixarenes; Conformation; Hydrolysis

Indexed keywords

CALIXARENE;

ALKYLATION; ARTICLE; CHEMICAL STRUCTURE; DEACYLATION; REACTION ANALYSIS; SUBSTITUTION REACTION; SYNTHESIS;

EID: 4544331213     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/ejoc.200400161     Document Type: Article

References (24)

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6. Calixarenes in Action (Eds.: L. Mandolini, R. Ungaro), Imperial College Press, London, 2000, and references cited therein.
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11. C. D. Gutsche, P. A. Reddy, J. Org. Chem. 1991, 56, 4783-4791.
12. K. Iwamoto, K. Araki, S. Shinkai, J. Org. Chem. 1991, 56, 4955-4962.
13. [8a] For a recent example see: J. Guillon, J.-M. Léger, P. Sonnet, C. Jarry, M. Robba, J. Org. Chem. 2000, 65, 8283-8289.
14. [8b] For a general synthetic protocol, see: W. Verboom, S. Datta, Z. Asfari, S. Harkema, D. N. Reinhoudt, J. Org. Chem. 1992, 57, 5394-5398.
15. For recent examples see: [9a] J. S. Kim, W. K. Lee, W. Sim, J. W. Ko, M. H. Cho, D. Y. Ra, J. W. Kim, J. Inclusion Phenom. Macrocycl. Chem. 2000, 37, 359-370.
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17. The symmetrical tribenzoyl, partial cone isomer was employed. For further details see ref. 11a.
18. [11a] A. W. Kleij, B. Souto, C. J. Pastor, P. Prados, J. de Mendoza, J. Org. Chem. 2003, 68, 8711-8714.
19. [11b] For a recent example of 1,2-disubstituted calix[4]arenes, see: F. Narumi, T. Hattori, N. Morohashi, N. Matsumura, W. Yamabuki, H. Kameyama, S. Miyano, Org. Biomol. Chem. 2004, 2, 890-898.
20. 3, room temp.) suggests a free rotation of the two free phenol sites. Note that the structure is inherently chiral and 2 exists therefore as a pair of enantiomers.
21. 1H NMR spectrum of the crude mixture.
22. 13C NMR spectroscopy is a useful tool for the conformation determination of calixarenes: C. Jaime, J. de Mendoza, P. Prados, P. M. Nieto, C. Sánchez, J. Org. Chem. 1991, 56, 3372-3376.
23. If stereochemical considerations were to play a predominant role, the 1,3-alt isomer 5 would be the major product in this particular reaction. The difference in conformational outcome for the alkylation process (propyl iodide vs. 4-methylbenzyl bromide) could be interpreted as the result of a competition between the rate of conformational interconversion and the rate of derivatization.
24. It has to be emphasized that only a single trituration step with MeOH was needed to separate the different calixarene conformers from the crude mixture. Received March 11, 2004