Supramolecular catalysis of unimolecular rearrangements: Substrate scope and mechanistic insights

Journal of the American Chemical Society

Volumn 128, Issue 31, 2006, Pages 10240-10252

  Fiedler, Dorothea ^a   Van Halbeek, Herman ^a   Bergman, Robert G ^a   Raymond, Kenneth N ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ENTROPY; HYDROLYSIS; PARAMETER ESTIMATION; POSITIVE IONS; REACTION KINETICS; SUBSTRATES; SUPRAMOLECULAR CHEMISTRY;

ALLYL ENAMMONIUM CATIONS; HYDROXIDES; IMINIUM PRODUCTS; SUPRAMOLECULAR STRUCTURES;

CATALYSIS;

ALLYL COMPOUND;

ARTICLE; ASYMMETRIC CATALYSIS; CHEMICAL REACTION; COVALENT BOND; ENTHALPY; ENTROPY; HYDROLYSIS; MOLECULAR INTERACTION; SOLUBILITY; SUPRAMOLECULAR CHEMISTRY; THERMODYNAMICS;

EID: 33746904317     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja062329b     Document Type: Article

References (61)

1. Cram, D. J. Angew. Chem., Int. Ed. Engl. 1988, 27, 1009-1020.
2. Lehn, J.-M. Angew. Chem., Int. Ed. Engl. 1988, 27, 89-112.
3. Takahashi, K. Chem. Rev. 1998, 98, 2013-2034.
4. Breslow, R.; Guo, T. J. Am. Chem. Soc. 1988, 110, 5613-5617.
5. Breslow, R.; Anslyn, E. J. Am. Chem. Soc. 1989, 111, 8931-8932.
6. Breslow, R.; Schmuck, C. J. Am. Chem. Soc. 1996, 118, 6601-6606.
7. Breslow, R.; Zhang, X.; Xu, R.; Maletic, M. J. Am. Chem. Soc. 1996, 118, 11678-11679.
8. Breslow, R.; Huang, Y.; Zhang, X.; Yang, J. Proc. Natl. Acad. Sci. U.S.A. 1997, 94, 11156-11158.
9. Breslow, R.; Dong, S. D. Chem. Rev. 1998, 98, 1997-2012.
10. Coolen, H. K. A. C.; van Leeuwen, P. W. N. M.; Nolle, R. J. M. J. Am. Chem. Soc. 1995, 117, 11906-11913.
11. Clyde-Watson, Z.; Vidal-Ferran, A.; Twyman, L. J.; Nakash, M.; Sanders, J. K. M. New J. Chem. 1998, 493-502.
12. Mattei, F.; Diederich, F. Helv. Chim. Acta 1997, 80, 1555-1588.
13. Yeh, R. M.; Davis, A. V.; Raymond, K. N. In Comprehensive Coordination Chemistry II; Meyer, T. J., Ed.; Elsevier Ltd.: Oxford, U.K., 2004; pp 327-355.
14. Hof, F.; Craig, S. L.; Nuckolls, C.; Rebek, J., Jr. Angew. Chem., Int. Ed. 2002, 41, 1488-1508.
15. Merlau, M. L.; Mejia, M. P.; Nguyen, S. T.; Hupp, J. T. Angew. Chem., Int. Ed. 2001, 40, 4239-4242.
16. Slagt, V. F.; Reek, J. N. H.; Kamer, P. C. J.; van Leeuwen, P. W. N. M. Angew. Chem., Int. Ed. 2001, 40, 4271-4274.
17. Slagt, V. F.; van Leeuwen, P. W. N. M.; Reek, J. N. H. Angew. Chem., Int. Ed. 2003, 42, 5619-5623.
18. Slagt, V. F.; Kamer, P. C. J.; van Leeuwen, P. W. N. M.; Reek, J. N. H. J. Am. Chem. Soc. 2004, 126, 1526-1536.
19. Slone, R. V.; Hupp, J. T. Inorg. Chem. 1997, 36, 5422-5423.
20. Wilkinson, M. J.; van Leeuwen, P. W. N. M.; Reek, J. N. H. Org. Biomol. Chem. 2005, 3, 2371-2383.
21. Kang, J. M.; Rebek, J., Jr. Nature 1997, 385, 50-52.
22. Kang, J. M.; Santamaria, J.; Hilmersson, G.; Rebek, J., Jr. J. Am. Chem. Soc. 1998, 120, 3650-3656.
23. Chen, J.; Rebek, J., Jr. Org. Lett. 2002, 4, 327-329.
24. Yoshizawa, M.; Takeyama, Y.; Kusukawa, T.; Fujita, M. Angew. Chem., Int. Ed. 2002, 41, 1347-1349.
25. Yoshizawa, M.; Takeyama, Y.; Okano, T.; Fujita, M. J. Am. Chem. Soc. 2003, 125, 3243-3247.
26. Ito, H.; Kusukawa, T.; Fujita, M. Chem. Lett. 2000, 598-599.
27. Fiedler, D.; Bergman, R. G.; Raymond, K. N. Angew. Chem., Int. Ed. 2004, 43, 6748-6751.
28. Caulder, D. L.; Powers, R. E.; Parac, T. N.; Raymond, K. N. Angew. Chem., Int. Ed. 1998, 37, 1840-1843.
29. Caulder, D. L.; Raymond, K. N. J. Chem. Soc., Dalton Trans. 1999, 1185-1200.
30. Caulder, D. L.; Brückner, C.; Powers, R. E.; König, S.; Parac, T. N.; Leary, J. A.; Raymond, K. N. J. Am. Chem. Soc. 2001, 123, 8923-8938.
31. Davis, A. V.; Raymond, K. N. J. Am. Chem. Soc. 2005, 127, 7912-7919.
32. Ziegler, M.; Davis, A. V.; Johnson, D. W.; Raymond, K. N. Angew. Chem., Int. Ed. 2003, 42, 665-668.
33. Terpin, A.; Ziegler, M.; Johnson, D. W.; Raymond, K. N. Angew. Chem., Int. Ed. 2001, 40, 157-160.
34. Fiedler, D.; Leung, D.; Bergman, R. G.; Raymond, K. N. J. Am. Chem. Soc. 2004, 126, 3674-3675.
35. Leung, D.; Fiedler, D.; Bergman, R. G.; Raymond, K. N. Angew. Chem., Int. Ed. 2004, 43, 963-966.
36. Walters, M. A. J. Org. Chem. 1996, 61, 978-983.
37. Przheval'skii, N. M.; Grandberg, I. I. Russ. Chem. Rev. 1987, 56, 477-491.
38. Elkik, E.; Francesch, C. Bull. Soc. Chim. 1968, 3, 903-910.
39. Opitz, G. Justus Liebigs Ann. Chem. 1961, 122-132.
40. Blechert, S. Synthesis 1989, 71-82.
41. Nubbemeyer, U. Top. Curr. Chem. 2005, 244, 149-213.
42. Enders, D.; Knopp, M.; Schiffers, R. Tetrahedron: Asymmetry 1996, 7, 1847-1882.
43. Nubbemeyer, U. Synthesis 2003, 7, 961-1008.
44. Jolidon, S.; Hansen, H.-J. Helv. Chim. Acta 1977, 60, 978-1032.
45. The short mixing time of 90 ms ensures that no correrlations due to spin diffusion are observed.
46. Neuhaus, D.; Williamson, M. P. The Nuclear Overhauser Effect in Structural and Confomational Analysis, 2nd ed.; VCH Publishers: New York, 2001.
47. + is a very weakly binding guest molecule and can easily be replaced by the entering enammonium substrates.
48. For several of the other substrates 2-9, iminium formation was also detected, but product 10i is unique in that its rate of formation is substantially greater than its rate of displacement from the cavity. Presumably, 10i has a higher binding constant for the cavity interior compared to those of the other iminium intermediates, which results in a longer lifetime.
49. Leung, D.; Bergman, R. G.; Raymond, K. N., unpublished results.
50. Hine, J.; Evangelista, R. A. J. Am. Chem. Soc. 1980, 102, 1649-1655.
51. Davis, A. V.; Fiedler, D.; Seeber, G.; Zahl, A.; van Eldik, R.; Raymond, K. N. J. Am. Chem. Soc. 2006, 128, 1324-1333.
52. Michels, M.; Raymond, K. N., unpublished results.
53. + was therefore limited.
54. Leung, D. H.; Bergman, R. G.; Raymond, K. N. J. Am. Chem. Soc., in press.
55. + is able to displace the iminium products from the cavity interior; concentration of the weakly bound 2i-8i can only build up in the absence of competing guest molecules.
56. Hiersemann, M.; Abraham, L. Eur. J. Org. Chem. 2002, 1461-1471.
57. Abraham, L.; Czerwonka, R.; Hiersemann, M. Angew. Chem., Int. Ed. 2001, 40, 4700-4703.
58. Caulder, D. L.; Powers, R. E.; Parac, T. N.; Raymond, K. N. Angew. Chem., Int. Ed. 1998, 37, 1840-1843.
59. Ellenberger, M. R.; Dixon, D. A.; Farneth, W. E. J. Am Chem. Soc. 1981, 103, 5377-5382.
60. Barta, N. S.; Cook, G. R.; Landis, M. S.; Stille, J. R. J. Org. Chem. 1992, 57, 7188-7194.
61. Perrin, D. D.; Dempsey, B. Buffers for pH and Metal Ion Control; Chapman and Hall: London, 1974.