Synthesis and structure of a bridged calix[6]arene with a sulfenic acid functionality in the cavity

Journal of Organic Chemistry

Volumn 61, Issue 9, 1996, Pages 2924-2925

  Saiki, Toshiyuki ^a   Goto, Kei ^a   Tokitoh, Norihiro ^a   Okazaki, Renji ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001290847     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960068q     Document Type: Article

References (32)

1. (a) Luning, U. Liebigs Ann. Chem. 1987, 949-955.
2. (b) Lüning, U Top. Curr. Chem. 1995, 175, 57-99 and references therein.
3. (a) Gutsche, C. D. In Calixarenes; Stoddart, J. F., Ed.; Royal Society of Chemistry: Cambridge, 1989.
4. (b) Vicens, J., Bohmer, V., Eds. Calixarenes: A Versatile Class of Macrocyclic Compounds; Kluwer Academic Publishers: Dordrecht, 1991.
5. (c) Böhmer, V. Angew. Chem., Int. Ed. Engl. 1995, 34, 713-745.
6. Tokitoh, N.; Saiki, T.; Okazaki, R. J. Chem. Soc., Chem. Commun. 1995, 1899-1900.
7. Very recently, Lüning et al. reported the concave pyridines bearing a framework similar to 1: Ross, H.; Lüning, U. Angew. Chem., Int. Ed. Engl. 1995, 34, 2555-2557.
8. For other examples of bridged or capped calix[6]arenes, see: (a) Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166. (b) Kanamathareddy, S.; Gutsche, C. D. J. Am. Chem. Soc. 1993, 115, 6572-6579. (c) Otsuka, H.; Araki, K.; Shinkai, S. J. Org. Chem. 1994, 59, 1542-1547. (d) Araki, K.; Akao, K.; Otsuka, H.; Nakashima, K.; Inokuchi, F.; Shinkai, S. Chem. Lett. 1994, 1251-1254. (e) Takeshita, M.; Nishio, S., Shinkai, S. J. Org. Chem. 1994, 59, 4032-4034. (f) Janssen, R. G.; Verboom, W.; van Duynhoven, J. P. M ; van Velzen, E. J. J.; Reinhoudt, D. N. Tetrahedron Lett. 1994, 35, 6555-6558. (g) Casnati, A.; Jacopozzi, P., Pochini, A.; Ugozzoli, F.; Cacciapaglia, R.; Mandolini, L.; Ungaro, R. Tetrahedron 1995, 51, 591-598.
9. For other examples of bridged or capped calix[6]arenes, see: (a) Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166. (b) Kanamathareddy, S.; Gutsche, C. D. J. Am. Chem. Soc. 1993, 115, 6572-6579. (c) Otsuka, H.; Araki, K.; Shinkai, S. J. Org. Chem. 1994, 59, 1542-1547. (d) Araki, K.; Akao, K.; Otsuka, H.; Nakashima, K.; Inokuchi, F.; Shinkai, S. Chem. Lett. 1994, 1251-1254. (e) Takeshita, M.; Nishio, S., Shinkai, S. J. Org. Chem. 1994, 59, 4032-4034. (f) Janssen, R. G.; Verboom, W.; van Duynhoven, J. P. M ; van Velzen, E. J. J.; Reinhoudt, D. N. Tetrahedron Lett. 1994, 35, 6555-6558. (g) Casnati, A.; Jacopozzi, P., Pochini, A.; Ugozzoli, F.; Cacciapaglia, R.; Mandolini, L.; Ungaro, R. Tetrahedron 1995, 51, 591-598.
10. For other examples of bridged or capped calix[6]arenes, see: (a) Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166. (b) Kanamathareddy, S.; Gutsche, C. D. J. Am. Chem. Soc. 1993, 115, 6572-6579. (c) Otsuka, H.; Araki, K.; Shinkai, S. J. Org. Chem. 1994, 59, 1542-1547. (d) Araki, K.; Akao, K.; Otsuka, H.; Nakashima, K.; Inokuchi, F.; Shinkai, S. Chem. Lett. 1994, 1251-1254. (e) Takeshita, M.; Nishio, S., Shinkai, S. J. Org. Chem. 1994, 59, 4032-4034. (f) Janssen, R. G.; Verboom, W.; van Duynhoven, J. P. M ; van Velzen, E. J. J.; Reinhoudt, D. N. Tetrahedron Lett. 1994, 35, 6555-6558. (g) Casnati, A.; Jacopozzi, P., Pochini, A.; Ugozzoli, F.; Cacciapaglia, R.; Mandolini, L.; Ungaro, R. Tetrahedron 1995, 51, 591-598.
11. For other examples of bridged or capped calix[6]arenes, see: (a) Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166. (b) Kanamathareddy, S.; Gutsche, C. D. J. Am. Chem. Soc. 1993, 115, 6572-6579. (c) Otsuka, H.; Araki, K.; Shinkai, S. J. Org. Chem. 1994, 59, 1542-1547. (d) Araki, K.; Akao, K.; Otsuka, H.; Nakashima, K.; Inokuchi, F.; Shinkai, S. Chem. Lett. 1994, 1251-1254. (e) Takeshita, M.; Nishio, S., Shinkai, S. J. Org. Chem. 1994, 59, 4032-4034. (f) Janssen, R. G.; Verboom, W.; van Duynhoven, J. P. M ; van Velzen, E. J. J.; Reinhoudt, D. N. Tetrahedron Lett. 1994, 35, 6555-6558. (g) Casnati, A.; Jacopozzi, P., Pochini, A.; Ugozzoli, F.; Cacciapaglia, R.; Mandolini, L.; Ungaro, R. Tetrahedron 1995, 51, 591-598.
12. For other examples of bridged or capped calix[6]arenes, see: (a) Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166. (b) Kanamathareddy, S.; Gutsche, C. D. J. Am. Chem. Soc. 1993, 115, 6572-6579. (c) Otsuka, H.; Araki, K.; Shinkai, S. J. Org. Chem. 1994, 59, 1542-1547. (d) Araki, K.; Akao, K.; Otsuka, H.; Nakashima, K.; Inokuchi, F.; Shinkai, S. Chem. Lett. 1994, 1251-1254. (e) Takeshita, M.; Nishio, S., Shinkai, S. J. Org. Chem. 1994, 59, 4032-4034. (f) Janssen, R. G.; Verboom, W.; van Duynhoven, J. P. M ; van Velzen, E. J. J.; Reinhoudt, D. N. Tetrahedron Lett. 1994, 35, 6555-6558. (g) Casnati, A.; Jacopozzi, P., Pochini, A.; Ugozzoli, F.; Cacciapaglia, R.; Mandolini, L.; Ungaro, R. Tetrahedron 1995, 51, 591-598.
13. For other examples of bridged or capped calix[6]arenes, see: (a) Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166. (b) Kanamathareddy, S.; Gutsche, C. D. J. Am. Chem. Soc. 1993, 115, 6572-6579. (c) Otsuka, H.; Araki, K.; Shinkai, S. J. Org. Chem. 1994, 59, 1542-1547. (d) Araki, K.; Akao, K.; Otsuka, H.; Nakashima, K.; Inokuchi, F.; Shinkai, S. Chem. Lett. 1994, 1251-1254. (e) Takeshita, M.; Nishio, S., Shinkai, S. J. Org. Chem. 1994, 59, 4032-4034. (f) Janssen, R. G.; Verboom, W.; van Duynhoven, J. P. M ; van Velzen, E. J. J.; Reinhoudt, D. N. Tetrahedron Lett. 1994, 35, 6555-6558. (g) Casnati, A.; Jacopozzi, P., Pochini, A.; Ugozzoli, F.; Cacciapaglia, R.; Mandolini, L.; Ungaro, R. Tetrahedron 1995, 51, 591-598.
14. For other examples of bridged or capped calix[6]arenes, see: (a) Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1992, 57, 3160-3166. (b) Kanamathareddy, S.; Gutsche, C. D. J. Am. Chem. Soc. 1993, 115, 6572-6579. (c) Otsuka, H.; Araki, K.; Shinkai, S. J. Org. Chem. 1994, 59, 1542-1547. (d) Araki, K.; Akao, K.; Otsuka, H.; Nakashima, K.; Inokuchi, F.; Shinkai, S. Chem. Lett. 1994, 1251-1254. (e) Takeshita, M.; Nishio, S., Shinkai, S. J. Org. Chem. 1994, 59, 4032-4034. (f) Janssen, R. G.; Verboom, W.; van Duynhoven, J. P. M ; van Velzen, E. J. J.; Reinhoudt, D. N. Tetrahedron Lett. 1994, 35, 6555-6558. (g) Casnati, A.; Jacopozzi, P., Pochini, A.; Ugozzoli, F.; Cacciapaglia, R.; Mandolini, L.; Ungaro, R. Tetrahedron 1995, 51, 591-598.
15. Goto, K.; Tokitoh, N.; Okazaki, R. Angew. Chem., Int. Ed. Engl. 1995, 34, 1124-1126.
16. For reviews on the chemistry of sulfenic acids, see: Hogg, D. R. In The Chemistry of Sulfenic Acids and Their Derivatives; Patai, S., Ed.; John Wiley & Sons: New York, 1990; pp 361-402. Kice, J. L. Adv. Phys. Org. Chem. 1980, 17, 65-181.
17. For reviews on the chemistry of sulfenic acids, see: Hogg, D. R. In The Chemistry of Sulfenic Acids and Their Derivatives; Patai, S., Ed.; John Wiley & Sons: New York, 1990; pp 361-402. Kice, J. L. Adv. Phys. Org. Chem. 1980, 17, 65-181.
18. For leading references on the biological reactions of sulfenic acids, see: (a) Allison, W. S. Acc. Chem. Res. 1976, 9, 293-299. (b) Claiborne, A.; Miller, H.; Parsonage, D.; Ross, R. P. FASEB J. 1993, 7, 1483-1490.
19. For leading references on the biological reactions of sulfenic acids, see: (a) Allison, W. S. Acc. Chem. Res. 1976, 9, 293-299. (b) Claiborne, A.; Miller, H.; Parsonage, D.; Ross, R. P. FASEB J. 1993, 7, 1483-1490.
20. A part of this work has been presented in 12th Symposium on Fundamental Organic Chemistry, Fukuoka, Japan, Oct 15-17, 1994, 2P36.
21. Davis, F. A.; Jenkins, L. A.; Billmers, R. L. J. Org. Chem. 1986, 51, 1033-1040.
22. 1H NMR spectra of 7 (25-120°C) are described in the supporting information.
23. 8 at 80°C for 4 h in a sealed tube indicated that both conformers of 6 disappeared at a similar rate.
24. 1H NMR data, see the supporting information.
25. 2O exchange experiment was unsuccessful because the signal at σ 2.39 appears only at high temperatures above ca. 100°C, where, in the presence of water, some decomposition of 7 was observed.
26. -1. The intensity data were collected on a Rigaku AFC7R diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.710 69 Å), and the structure was solved by direct methods and expanded using Fourier techniques. The bridging m-xylene moiety including the SOH group exhibited inversional disorder with regard to the center of symmetry, while the structure of calix[6]arene moiety was found common to both of the disordered molecules. Some non-hydrogen atoms were refined anisotropically, while the rest were refined isotropically Hydrogen atoms except for those of the SOH group and the solvent were included but not refined. The final cycle of full-matrix least-squares refinement was based on 1948 observed reflections [I > 3.00σ(I)] and 336 variable parameters with R (Rw) = 0.117 (0.135). The author has deposited atomic coordinates for 7 with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK.
27. For X-ray analysis of an alkanesulfenic acid, two examples have been reported: (a) Kato, K. Acta Crystallogr., Sect. B. 1972, 28, 55-59. (b) Tripolt, R.; Belaj, F ; Nachbaur, E. Z. Naturforsch., Sect. B 1993, 48, 1212-1222. The X-ray structure of 9-triptycenesulfenic acid has also been determined, although not published: Nakamura, N. Private communication.
28. For X-ray analysis of an alkanesulfenic acid, two examples have been reported: (a) Kato, K. Acta Crystallogr., Sect. B. 1972, 28, 55-59. (b) Tripolt, R.; Belaj, F ; Nachbaur, E. Z. Naturforsch., Sect. B 1993, 48, 1212-1222. The X-ray structure of 9-triptycenesulfenic acid has also been determined, although not published: Nakamura, N. Private communication.
29. For X-ray analysis of an alkanesulfenic acid, two examples have been reported: (a) Kato, K. Acta Crystallogr., Sect. B. 1972, 28, 55-59. (b) Tripolt, R.; Belaj, F ; Nachbaur, E. Z. Naturforsch., Sect. B 1993, 48, 1212-1222. The X-ray structure of 9-triptycenesulfenic acid has also been determined, although not published: Nakamura, N. Private communication.
30. For the conformational notations, see ref 5b.
31. The preliminary results for the bond lengths (Å), bond angles (deg), and torsion angle (deg) around the sulfenic acid group: S(1)-O(1), 1.58(3); S(1)-C(1), 1.75(3); O(1)-S(1)-C(1), 107(1); C(6)*-C(1)-S(1)-O(1), 72(2).
32. The generation of 10 was confirmed by a trapping experiment with methyl propiolate.