The room-temperature stabilization of bicyclo[2.2.2]oct-1-ene and bicyclo[3.2.1]oct-1-ene

Angewandte Chemie - International Edition

Volumn 42, Issue 26, 2003, Pages 3039-3042

  Roach, Paul ^b   Warmuth, Ralf ^a  

^a RUTGERS UNIVERSITY   (United States)

^b NOTTINGHAM TRENT UNIVERSITY   (United Kingdom)

Author keywords

Carbenes; Hemicarcerands; Host guest systems; Ring expansion; Strained molecules

Indexed keywords

DIMERIZATION; PHOTOCHEMICAL REACTIONS; REACTION KINETICS;

INCARCERATION;

OLEFINS;

BICYCLO COMPOUND; BICYCLO[2.2.2]OCT 1 ENE; BICYCLO[3.2.1]OCT 1 ENE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; DIELS ALDER REACTION; DIMERIZATION; MOLECULAR STABILITY; PHOTOCHEMICAL EFFICIENCY; PHOTOCHEMISTRY; ROOM TEMPERATURE; TEMPERATURE DEPENDENCE;

EID: 0042307366     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200351120     Document Type: Article

References (42)

1. J. Bredt, H. Thouet, L. Schmitz, Justus Liebigs Ann. Chem. 1924, 437, 1.
2. a) P. M. Warner, Chem. Rev. 1989, 89, 1067;
3. b) H. Hopf, Classics in Hydrocarbon Chemistry, Wiley-VCH, Weinheim, 2000, p. 122.
4. W.F. Maier, P. von, R. Schleyer, J. Am. Chem. Soc. 1981, 103, 1891.
5. a) J. R. Wiseman, J. A. Chong, J. Am. Chem. Soc. 1969, 91, 7775;
6. b) M. S. Gudipati, J. G. Radziszewski, P. Kaszynski, J. Michl, J. Org. Chem. 1993, 58, 3668.
7. S. F. Sellers, T. C. Klebach, E Hollywood, M. Jones, Jr., J. Am. Chem. Soc. 1982, 104, 7075;
8. b) K. Hirai, H. Tomioka, T. Okazaki, K. Tokunaga, T. Kitagawa, K. Takeuchi, J. Phys. Org. Chem. 1999, 12, 165;
9. c) M. Ohno, M. Itoh, M. Umeda, R. Furuta, K. Kondo, S. Equchi, J. Am. Chem. Soc. 1996, 118, 4981.
10. E. L. Tae, Z. Zhu, M. S. Platz, J. Phys. Chem. A 2001, 105, 3803.
11. a) A. D. Wolf, M. Jones, Jr., J. Am. Chem. Soc. 1973, 95, 8209;
12. b) N. Bian, M. Jones, Jr., Tetrahedron Lett. 1993, 34, 3967;
13. c) R. T. Ruck, M. Jones, Jr., Tetrahedron Lett. 1998, 39, 4433.
14. C. M. Geise, C. M. Hadad, J. Am. Chem. Soc. 2000, 122, 5861.
15. a) D. J. Cram, J. M. Cram, Container Molecules and Their Guests (Ed.: J. F. Stoddart), The Royal Society of Chemistry, Cambridge, UK, 1994;
16. b) A. Jasat, J. C. Sherman, Chem. Rev. 1999, 99, 931.
17. a) D. J. Cram, M. E. Tanner, R. Thomas, Angew. Chem. 1991, 103, 1048; Angew. Chem. Int. Ed. Engl. 1991, 30, 1024;
18. a) D. J. Cram, M. E. Tanner, R. Thomas, Angew. Chem. 1991, 103, 1048; Angew. Chem. Int. Ed. Engl. 1991, 30, 1024;
19. b) R. Warmuth, Angew. Chem. 1997, 109, 1406; Angew. Chem. Int. Ed. Engl. 1997, 36, 1347;
20. b) R. Warmuth, Angew. Chem. 1997, 109, 1406; Angew. Chem. Int. Ed. Engl. 1997, 36, 1347;
21. c) R. Warmuth, J. Chem. Soc. Chem. Commun. 1998, 59;
22. d) R. Warmuth, M. A. Marvel, Angew. Chem. 2000, 112, 1168; Angew. Chem. Int. Ed. 2000, 39, 1117;
23. d) R. Warmuth, M. A. Marvel, Angew. Chem. 2000, 112, 1168; Angew. Chem. Int. Ed. 2000, 39, 1117;
24. e) R. Warmuth, M. A. Marvel, Chem. Eur. J. 2001, 7, 1209;
25. f) R. Warmuth, J. Am. Chem. Soc. 2001,123, 6955;
26. g) J.-L. Kerdelhué, K. J. Langenwalter, R. Warmuth, J. Am. Chem. Soc. 2003, 125, 973.
27. For related reactions inside cyclodextrins, see: a) U. H. Brinker, R. Buchkremer, M. G. Rosenberg, M. D. Poliks, M. Orlando, M. L. Gross, Angew. Chem. 1993, 105, 1427; Angew. Chem. Int. Ed. Engl. 1993, 32, 1344;
28. For related reactions inside cyclodextrins, see: a) U. H. Brinker, R. Buchkremer, M. G. Rosenberg, M. D. Poliks, M. Orlando, M. L. Gross, Angew. Chem. 1993, 105, 1427; Angew. Chem. Int. Ed. Engl. 1993, 32, 1344;
29. b) U. H. Brinker, M. G. Rosenberg in Advances in Carbene Chemistry, Vol. 2 (Ed.: U. H. Brinker), Jai, London, 1998, p. 29.
30. K. Kostova, V. Dimitrov, Synth. Commun. 1995, 25, 1575.
31. I. R. Likhotvorik, E. L. Tae, C. Ventre, M. S. Platz, Tetrahedron Lett. 2000, 41, 795.
32. 1H NMR spectrum of the product mixture.
33. H. O. House, R. J. Outcalt, J. L. Haack, D. van der Veer, J. Org. Chem. 1983, 48, 1654.
34. M. T. H. Liu, Chem. Soc. Rev. 1982, 11, 127.
35. max = 310 nm, the photosensitivity of 1 below 335 nm is not surprising.
36. The life-time of trans-1-phenylcyclohexene is 9 μs at room temperature: L. Bonneau, J. Joussot-Dubien, L. Salem, A. J. Yarwood, J. Am. Chem. Soc. 1976, 98, 4329.
37. a) A. M. A. van Wageningen, P. Timmerman, J. P. M. van Duynhoven, W. Verboom, F. C. J. M. van Veggel, D. N. Reinhoudt, Chem. Eur. J. 1997, 3, 639;
38. b) S. K. Körner, F. C. Tucci, D. M. Rudkevich, T. Heinz, J. Rebek, Jr., Chem. Eur. J. 2000, 6, 188.
39. a) G. Jenner, J. Rimmelin, Tetrahedron Lett. 1980, 21, 3039;
40. b) R. van Eldik, T. Asano, W. J. LeNoble, Chem. Rev. 1989, 89, 549.
41. The amount of 5 ⊙ 1 was determined from the amount of free 4, which formed under these conditions by the retro-Diels-Alder reaction of 1 followed by the dissociation of 5 ⊙ 4.
42. [7c] The latter would isomerize to (Z)-2 prior to its retro-Diels-Alder reaction. (Z)-2 is a thermodynamic sink under these conditions and is unlikely to rearrange to 4 (life-time of 5 ⊙ (Z)-2 = 4.4 h at 197°C).