Selective functionalization of a single methylene bridge of a Calix[6]arene

Journal of Organic Chemistry

Volumn 75, Issue 10, 2010, Pages 3437-3442

  Itzhak, Norbert ^a   Biali, Silvio E ^a  

^a HEBREW UNIVERSITY OF JERUSALEM   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

ARENE DERIVATIVES; CALIX[6]ARENES; CHLORO DERIVATIVES; FUNCTIONALIZED; METHYLENE BRIDGE; SELECTIVE FUNCTIONALIZATION; SYNTHETIC INTERMEDIATES;

CALIXARENE; CARBENE; MACROCYCLIC COMPOUND;

ARTICLE; BROMINATION; CHEMICAL REACTION; CONFORMATION; CRYSTAL STRUCTURE; NUCLEAR MAGNETIC RESONANCE; SYNTHESIS;

CALIXARENES; CRYSTALLOGRAPHY, X-RAY; MODELS, MOLECULAR; MOLECULAR STRUCTURE; PHENOLS; PHOTOCHEMISTRY;

EID: 77952520907     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo1005476     Document Type: Article

References (40)

1. For recent reviews on calixarenes, see: Calixarenes in Action; Mandolini, L., Ungaro, R., Eds.; Imperial College Press: London, 2000.
2. Böhmer, V. In The Chemistry of Phenols; Rappoport, Z., Ed.; Wiley: Chichester, 2003; Chapter 19.
3. Gutsche, C. D. Calixarenes: an Introduction; Royal Society of Chemistry: Cambridge, 2008.
4. For recent examples, see: Troisi, F.; Mogavero, L.; Gaeta, C.; Gavuzzo, E.; Neri, P. Org. Lett. 2007, 9, 915
5. Troisi, F.; Citro, L; Gaeta, C.; Gavuzzo, E.; Neri, P. Org. Lett. 2008, 10, 1393
6. Tabatabai, M.; Vogt, W.; Böhmer, V. Tetrahedron Lett. 1990, 31, 3295
7. Sartori, G.; Maggi, R.; Bigi, F.; Arduini, A.; Pastorio, A.; Porta, C. J. Chem. Soc., Perkin Trans. 1 1994, 1657
8. 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, 2261
9. Bergamaschi, M.; Bigi, F.; Lanfranchi, M.; Maggi, R.; Pastorio, A.; Pellinghelli, M. A.; Peri, F.; Porta, C.; Sartori, G. Tetrahedron 1997, 53, 13037
10. For a review on the synthesis of calixarenes via the stepwise and fragment condensation methods, see: Böhmer, V. Liebigs Ann./Recueil 1997, 2019
11. Middel, O.; Greff, Z.; Taylor, N. J.; Verboom, W.; Reinhoudt, D. N.; Snieckus, V. J. Org. Chem. 2000, 65, 667
12. Scully, P. A.; Hamilton, T. M.; Bennett, J. L. Org. Lett. 2001, 3, 2741
13. Hertel, M. P.; Behrle, A. C.; Williams, S. A.; Schmidt, J. A. R.; Fantini, J. L. Tetrahedron 2009, 65, 8657. J. L. Fantini previously published as J. L. Bennett.
14. For a recent study of the conformation behavior of a calix[4]arene with a single methylene group substituted by a carboxyl functionality, see: Gruber, T.; Gruner, M.; Fischer, C.; Seichter, W.; Bombicz, P.; Weber, E. New J. Chem. 2010, 34, 250
15. For agostic and methylene hydride complexes of calix[4]arene, see: Buccella, D.; Parkin, G. J. Am. Chem. Soc. 2006, 128, 16358
16. For examples of calixarenes modified at two or all bridges, see, for example: Görmar, G.; Seiffarth, K.; Schultz, M.; Zimmerman, J.; Flämig, G. Makromol. Chem. 1990, 191, 81
17. Agbaria, K.; Biali, S. E. J. Am. Chem. Soc. 2001, 123, 12495
18. Kuno, L.; Seri, N.; Biali, S. E. Org. Lett. 2007, 9, 1577
19. For a recent example of an optically active methylene-substituted calix[4]arene, see: Gopalsamuthiram, V.; Predeus, A. V.; Huang, R. H.; Wulff, W. D. J. Am. Chem. Soc. 2009, 131, 18018
20. Klenke, B.; Näther, C.; Friedrichsen, W. Tetrahedron Lett. 1998, 39, 8967
21. Kumar, S. K.; Chawla, H. M.; Varadarajan, R. Tetrahedron Lett. 2002, 43, 7073
22. Columbus, I.; Biali, S. E. Org. Lett. 2007, 9, 2927
23. Columbus, I.; Biali, S. E. J. Org. Chem. 2008, 73, 2598
24. Kogan, K.; Columbus, I.; Biali, S. E. J. Org. Chem. 2008, 73, 7327
25. Kogan, K.; Biali, S. E. J. Org. Chem. 2009, 74, 7172
26. For examples of silver-mediated substitutions in bromodienone calixarene derivatives, see: Troisi, F.; Pierro, T.; Gaeta, C.; Neri, P. Org. Lett. 2009, 11, 697
27. Several calix[5]arenes monosubstituted at a single bridge have been prepared by the fragment condensation method. See: Biali, S. E.; Böhmer, V.; Columbus, I; Ferguson, G.; Grüttner, C.; Grynszpan, F.; Paulus, E. F.; Thondorf, I. J. Chem. Soc., Perkin Trans. 2 1998, 2261
28. Justus, K.; Beck, T.; Noltemeyer, M.; Fitjer, L. Tetrahedron 2009, 65, 5192
29. Seri, N.; Thondorf, I.; Biali, S. E. J. Org. Chem. 2004, 69, 4774
30. Kogan, K.; Biali, S. E. Org. Lett. 2007, 9, 2393
31. The use of 4b as a starting material for the preparation of methylene-functionalized calix[8]arenes is currently under investigation and will be reported in due course.
32. 2 to 188 K resulted in extensive broadening of all signals, but no decoalescence was observed.
33. In contrast to 1c, the reaction of 5 with aniline (in HFIP) proceeds in nonregioselective fashion and affords a mixture of two products, derived from N-alkylation and C-alkylation of aniline.
34. Hofmann, M.; Hampel, N.; Kanzian, T.; Mayr, H. Angew. Chem. Int. Ed. 2004, 43, 5402
35. In principle, reaction of the carbocation with TFE could results in the formation of 6a. However, if the trifluoroethoxy group of 6a is reversibly cleaved under the acidic reaction conditions, but the electrophilic substitution reaction on the aromatic ring is irreversible, only the Friedel-Crafts product should be obtained.
36. For recent reports of the Lewis acid-catalyzed alkylation of benzhydryl cations with compounds possessing active methylenes, see: Bisaro, F.; Prestat, G.; Vitale, M.; Poli, G. Synlett 2002, 1823
37. Jana, U.; Biswas, S.; Maiti, S. Tetrahedron Lett. 2007, 48, 4066
38. Sanz, R.; Miguel, D.; Martinez, A.; Alvarez-Gutierrez, J. M.; Rodriguez, F. Org. Lett. 2007, 9, 2027
39. Middleton, W. J. J. Org. Chem. 1975, 40, 574
40. Janssen, R. G.; Verboom, W.; Reinhoudt, D. N.; Casnati, A.; Freriks, M.; Pochini, A.; Ugozzoli, F.; Ungaro, R.; Nieto, P. M.; Carramolino, M.; Cuevas, F.; Prados, P.; de Mendoza, J. Synthesis 1993, 380