Catalysis by organic solids. Stereoselective Diels-Alder reactions promoted by microporous molecular crystals having an extensive hydrogen- bonded network

Journal of the American Chemical Society

Volumn 119, Issue 18, 1997, Pages 4117-4122

  Endo, Ken ^a   Koike, Takashi ^a   Sawaki, Tomoya ^a   Hayashida, Osamu ^a,b   Masuda, Hideki ^b,c   Aoyama, Yasuhiro ^a,b  

^a KYUSHU UNIVERSITY   (Japan)

^b JAPAN SCIENCE AND TECHNOLOGY AGENCY   (Japan)

^c NAGOYA INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACRYLIC ACID; ANTHRACENE DERIVATIVE; RESORCINOL DERIVATIVE; ZEOLITE;

ARTICLE; CATALYSIS; CRYSTAL; CRYSTAL STRUCTURE; HYDROGEN BOND; STEREOCHEMISTRY; X RAY CRYSTALLOGRAPHY;

EID: 0031003197     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja964198s     Document Type: Article

References (72)

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19. For selected examples, see: (a) Barrer, R. M.; Shanson, V. H. J. Chem. Soc., Chem. Commun. 1976, 333-334. (b) Ermer, O. J. Am. Chem. Soc. 1988, 110, 3747-3754. (c) Weber, E.; Pollex, R.; Czugler, M. J. Org. Chem. 1992, 57, 4068-4070. (d) Copp, S. B.; Subramanian, S.; Zaworotko, M. J. Ibid. 1992, 114, 8719-8720. (e) Reddy, D. S.; Craig, D. C.; Rae, A. D.; Desiraju, G. R. J. Chem. Soc., Chem. Commun. 1993, 1737-1739. (f) Wang, X.; Simard, M.; Wuest, J. D. J. Am. Chem. Soc. 1994, 116, 12119-12120. (g) Venkataraman, D.; Lee, S.; Zhang, J.; Moore, J. S. Nature 1994, 371, 591-593. (h) Reddy, D. S.; Craig, D. C.; Desiraju, G. R. J. Am. Chem. Soc. 1996, 118, 4090-4093.
20. For selected examples, see: (a) Barrer, R. M.; Shanson, V. H. J. Chem. Soc., Chem. Commun. 1976, 333-334. (b) Ermer, O. J. Am. Chem. Soc. 1988, 110, 3747-3754. (c) Weber, E.; Pollex, R.; Czugler, M. J. Org. Chem. 1992, 57, 4068-4070. (d) Copp, S. B.; Subramanian, S.; Zaworotko, M. J. Ibid. 1992, 114, 8719-8720. (e) Reddy, D. S.; Craig, D. C.; Rae, A. D.; Desiraju, G. R. J. Chem. Soc., Chem. Commun. 1993, 1737-1739. (f) Wang, X.; Simard, M.; Wuest, J. D. J. Am. Chem. Soc. 1994, 116, 12119-12120. (g) Venkataraman, D.; Lee, S.; Zhang, J.; Moore, J. S. Nature 1994, 371, 591-593. (h) Reddy, D. S.; Craig, D. C.; Desiraju, G. R. J. Am. Chem. Soc. 1996, 118, 4090-4093.
21. For selected examples, see: (a) Barrer, R. M.; Shanson, V. H. J. Chem. Soc., Chem. Commun. 1976, 333-334. (b) Ermer, O. J. Am. Chem. Soc. 1988, 110, 3747-3754. (c) Weber, E.; Pollex, R.; Czugler, M. J. Org. Chem. 1992, 57, 4068-4070. (d) Copp, S. B.; Subramanian, S.; Zaworotko, M. J. Ibid. 1992, 114, 8719-8720. (e) Reddy, D. S.; Craig, D. C.; Rae, A. D.; Desiraju, G. R. J. Chem. Soc., Chem. Commun. 1993, 1737-1739. (f) Wang, X.; Simard, M.; Wuest, J. D. J. Am. Chem. Soc. 1994, 116, 12119-12120. (g) Venkataraman, D.; Lee, S.; Zhang, J.; Moore, J. S. Nature 1994, 371, 591-593. (h) Reddy, D. S.; Craig, D. C.; Desiraju, G. R. J. Am. Chem. Soc. 1996, 118, 4090-4093.
22. For selected examples, see: (a) Barrer, R. M.; Shanson, V. H. J. Chem. Soc., Chem. Commun. 1976, 333-334. (b) Ermer, O. J. Am. Chem. Soc. 1988, 110, 3747-3754. (c) Weber, E.; Pollex, R.; Czugler, M. J. Org. Chem. 1992, 57, 4068-4070. (d) Copp, S. B.; Subramanian, S.; Zaworotko, M. J. Ibid. 1992, 114, 8719-8720. (e) Reddy, D. S.; Craig, D. C.; Rae, A. D.; Desiraju, G. R. J. Chem. Soc., Chem. Commun. 1993, 1737-1739. (f) Wang, X.; Simard, M.; Wuest, J. D. J. Am. Chem. Soc. 1994, 116, 12119-12120. (g) Venkataraman, D.; Lee, S.; Zhang, J.; Moore, J. S. Nature 1994, 371, 591-593. (h) Reddy, D. S.; Craig, D. C.; Desiraju, G. R. J. Am. Chem. Soc. 1996, 118, 4090-4093.
23. For selected examples, see: (a) Barrer, R. M.; Shanson, V. H. J. Chem. Soc., Chem. Commun. 1976, 333-334. (b) Ermer, O. J. Am. Chem. Soc. 1988, 110, 3747-3754. (c) Weber, E.; Pollex, R.; Czugler, M. J. Org. Chem. 1992, 57, 4068-4070. (d) Copp, S. B.; Subramanian, S.; Zaworotko, M. J. Ibid. 1992, 114, 8719-8720. (e) Reddy, D. S.; Craig, D. C.; Rae, A. D.; Desiraju, G. R. J. Chem. Soc., Chem. Commun. 1993, 1737-1739. (f) Wang, X.; Simard, M.; Wuest, J. D. J. Am. Chem. Soc. 1994, 116, 12119-12120. (g) Venkataraman, D.; Lee, S.; Zhang, J.; Moore, J. S. Nature 1994, 371, 591-593. (h) Reddy, D. S.; Craig, D. C.; Desiraju, G. R. J. Am. Chem. Soc. 1996, 118, 4090-4093.
24. For selected examples, see: (a) Barrer, R. M.; Shanson, V. H. J. Chem. Soc., Chem. Commun. 1976, 333-334. (b) Ermer, O. J. Am. Chem. Soc. 1988, 110, 3747-3754. (c) Weber, E.; Pollex, R.; Czugler, M. J. Org. Chem. 1992, 57, 4068-4070. (d) Copp, S. B.; Subramanian, S.; Zaworotko, M. J. Ibid. 1992, 114, 8719-8720. (e) Reddy, D. S.; Craig, D. C.; Rae, A. D.; Desiraju, G. R. J. Chem. Soc., Chem. Commun. 1993, 1737-1739. (f) Wang, X.; Simard, M.; Wuest, J. D. J. Am. Chem. Soc. 1994, 116, 12119-12120. (g) Venkataraman, D.; Lee, S.; Zhang, J.; Moore, J. S. Nature 1994, 371, 591-593. (h) Reddy, D. S.; Craig, D. C.; Desiraju, G. R. J. Am. Chem. Soc. 1996, 118, 4090-4093.
25. (a) For a list of recent publications on the formation of ordered crystal structures involving hydrogen-bonded 1D, 2D, and 3D motifs, see: Aoyama, Y.; Endo, K.; Anzai, T.; Yamaguchi, Y.; Sawaki, T.; Kobayashi, K.; Kanehisa, N.; Hashimoto, H.; Kai, Y.; Masuda, H. J. Am. Chem. Soc. 1996, 118, 5562-5571.
26. Also see: (b) MacDonald, J. C.; Whitesides, G. M. Chem. Rev. 1994, 94, 2383-2420.
27. (c) Valiyaveettil, S.; Enkelmann, V.; Mülln, K. J. Chem. Soc., Chem. Commun. 1994, 2097-2098.
28. (d) Hosseini, M. W.; Ruppert, R.; Schaeffer, P.; De Cian, A.; Kyritsakas, N.; Fischer, J. Ibid. 1994, 2135-2136.
29. For examples of (infinite) metal-coodination networks, see: (e) Abrahams, B. F.; Hoskins, B. F.; Liu, J.; Robson, R. J. Am. Chem. Soc. 1991, 113, 3045-3051.
30. (f) Reference 3c.
31. (g) Reference 5d.
32. (h) Stang, P. J.; Cao, D. H.; Saito, S.; Arif, A. M. Ibid. 1995, 117, 6273-6283.
33. (i) Fujita, M.; Kwon, Y. J.; Sasaki, O.; Yamaguchi, K.; Ogura, K. Ibid. 1995, 117, 7287-7288.
34. Cf., Endo, K.; Ezuhara, T.; Koyanagi, M.; Masuda, H.; Aoyama, Y. J. Am. Chem. Soc. 1997, 119, 499-505.
35. (a) Reference 2.
36. (b) Endo, K.; Sawaki, T.; Koyanagi, M.; Kobayashi, K.; Masuda, H.; Aoyama, Y. J. Am. Chem. Soc. 1995, 117, 8341-8352.
37. (c) Reference 6a.
38. Kobayashi, K.; Endo, K.; Aoyama, Y.; Masuda, H. Tetrahedron Lett. 1993, 34, 7929-2932.
39. Diels - Alder reactions have been demonstrated to occur in the solid state by cocrystallization of diene and dienophile: Kishan, K. V. R.; Desiraju, G. R. J. Org. Chem. 1987, 52, 4641-4644. Also see: Sergeev, G. B.; Komarov, V. S.; Zvonov, A. V. Dokl. Akad. Nauk SSSR 1983, 270, 139-142.
40. Diels - Alder reactions have been demonstrated to occur in the solid state by cocrystallization of diene and dienophile: Kishan, K. V. R.; Desiraju, G. R. J. Org. Chem. 1987, 52, 4641-4644. Also see: Sergeev, G. B.; Komarov, V. S.; Zvonov, A. V. Dokl. Akad. Nauk SSSR 1983, 270, 139-142.
41. For Diels - Alder reactions in the host - guest systems, see: (a) Walter, C. J.; Anderson, H. L.; Sanders, J. K. M. J. Chem. Soc., Chem. Commun. 1993, 458-460 (high exo-selectivity). (b) Hirst, S. C.; Hamilton, A. D. J. Am. Chem. Soc. 1991, 113, 382-383 (intramolecular reaction). (c) Sternbach, D. D.; Rossana, D. M. Ibid. 1982, 104, 5853-5854 (intramolecular reaction). (d) Rideout, D. C.; Breslow, R. Ibid. 1980, 102, 7816-7817 (hydrophobic acceleration). For other pericyclic reactions, see; (e) Mock, W. C.; Irra, T. A.; Wepsiec, J. P.; Adhya, M. J. Org. Chem. 1989, 54, 5302-5308. (f) Ueno, A.; Moriwaki, F.; Iwama, Y.; Suzuki, I.; Osa, T.; Ohta, T.; Nozoe, S. J. Am. Chem. Soc. 1991, 113, 7034-7036.
42. For Diels - Alder reactions in the host - guest systems, see: (a) Walter, C. J.; Anderson, H. L.; Sanders, J. K. M. J. Chem. Soc., Chem. Commun. 1993, 458-460 (high exo-selectivity). (b) Hirst, S. C.; Hamilton, A. D. J. Am. Chem. Soc. 1991, 113, 382-383 (intramolecular reaction). (c) Sternbach, D. D.; Rossana, D. M. Ibid. 1982, 104, 5853-5854 (intramolecular reaction). (d) Rideout, D. C.; Breslow, R. Ibid. 1980, 102, 7816-7817 (hydrophobic acceleration). For other pericyclic reactions, see; (e) Mock, W. C.; Irra, T. A.; Wepsiec, J. P.; Adhya, M. J. Org. Chem. 1989, 54, 5302-5308. (f) Ueno, A.; Moriwaki, F.; Iwama, Y.; Suzuki, I.; Osa, T.; Ohta, T.; Nozoe, S. J. Am. Chem. Soc. 1991, 113, 7034-7036.
43. For Diels - Alder reactions in the host - guest systems, see: (a) Walter, C. J.; Anderson, H. L.; Sanders, J. K. M. J. Chem. Soc., Chem. Commun. 1993, 458-460 (high exo-selectivity). (b) Hirst, S. C.; Hamilton, A. D. J. Am. Chem. Soc. 1991, 113, 382-383 (intramolecular reaction). (c) Sternbach, D. D.; Rossana, D. M. Ibid. 1982, 104, 5853-5854 (intramolecular reaction). (d) Rideout, D. C.; Breslow, R. Ibid. 1980, 102, 7816-7817 (hydrophobic acceleration). For other pericyclic reactions, see; (e) Mock, W. C.; Irra, T. A.; Wepsiec, J. P.; Adhya, M. J. Org. Chem. 1989, 54, 5302-5308. (f) Ueno, A.; Moriwaki, F.; Iwama, Y.; Suzuki, I.; Osa, T.; Ohta, T.; Nozoe, S. J. Am. Chem. Soc. 1991, 113, 7034-7036.
44. For Diels - Alder reactions in the host - guest systems, see: (a) Walter, C. J.; Anderson, H. L.; Sanders, J. K. M. J. Chem. Soc., Chem. Commun. 1993, 458-460 (high exo-selectivity). (b) Hirst, S. C.; Hamilton, A. D. J. Am. Chem. Soc. 1991, 113, 382-383 (intramolecular reaction). (c) Sternbach, D. D.; Rossana, D. M. Ibid. 1982, 104, 5853-5854 (intramolecular reaction). (d) Rideout, D. C.; Breslow, R. Ibid. 1980, 102, 7816-7817 (hydrophobic acceleration). For other pericyclic reactions, see; (e) Mock, W. C.; Irra, T. A.; Wepsiec, J. P.; Adhya, M. J. Org. Chem. 1989, 54, 5302-5308. (f) Ueno, A.; Moriwaki, F.; Iwama, Y.; Suzuki, I.; Osa, T.; Ohta, T.; Nozoe, S. J. Am. Chem. Soc. 1991, 113, 7034-7036.
45. For Diels - Alder reactions in the host - guest systems, see: (a) Walter, C. J.; Anderson, H. L.; Sanders, J. K. M. J. Chem. Soc., Chem. Commun. 1993, 458-460 (high exo-selectivity). (b) Hirst, S. C.; Hamilton, A. D. J. Am. Chem. Soc. 1991, 113, 382-383 (intramolecular reaction). (c) Sternbach, D. D.; Rossana, D. M. Ibid. 1982, 104, 5853-5854 (intramolecular reaction). (d) Rideout, D. C.; Breslow, R. Ibid. 1980, 102, 7816-7817 (hydrophobic acceleration). For other pericyclic reactions, see; (e) Mock, W. C.; Irra, T. A.; Wepsiec, J. P.; Adhya, M. J. Org. Chem. 1989, 54, 5302-5308. (f) Ueno, A.; Moriwaki, F.; Iwama, Y.; Suzuki, I.; Osa, T.; Ohta, T.; Nozoe, S. J. Am. Chem. Soc. 1991, 113, 7034-7036.
46. For Diels - Alder reactions in the host - guest systems, see: (a) Walter, C. J.; Anderson, H. L.; Sanders, J. K. M. J. Chem. Soc., Chem. Commun. 1993, 458-460 (high exo-selectivity). (b) Hirst, S. C.; Hamilton, A. D. J. Am. Chem. Soc. 1991, 113, 382-383 (intramolecular reaction). (c) Sternbach, D. D.; Rossana, D. M. Ibid. 1982, 104, 5853-5854 (intramolecular reaction). (d) Rideout, D. C.; Breslow, R. Ibid. 1980, 102, 7816-7817 (hydrophobic acceleration). For other pericyclic reactions, see; (e) Mock, W. C.; Irra, T. A.; Wepsiec, J. P.; Adhya, M. J. Org. Chem. 1989, 54, 5302-5308. (f) Ueno, A.; Moriwaki, F.; Iwama, Y.; Suzuki, I.; Osa, T.; Ohta, T.; Nozoe, S. J. Am. Chem. Soc. 1991, 113, 7034-7036.
47. Solid-state photodimerization of olefins is well-known and is also relevant to the present reactions (reference 1). Also see: Granagura, K.; Ramasubbu, N.; Verkatesan, K.; Ramamurthy, V. J. Org. Chem. 1985, 50, 2337-2346.
48. The slope of the yield - time plots (Figure 1) at an early stage of the reaction corresponds to the pseudo-first-order rate constant, the accurate value of which can also be obtained by the standard pseudo-first-order treatment of the kinetic data.
49. This treatment of homogeneous kinetic data is only for the purpose of comparison with heterogeneous kinetic data; it is difficult to define concentration for an insoluble catalyst.
50. -1 (Figure 2). Further addition of resorcinol results in its precipitation without causing any notable increase in the rate.
51. 6).
52. w = 0.070.
53. One of the problems, especially tor the acrolein system, is spontaneous desorption of included cyclohexadiene from the isolated adducts. Thus, the adducts undergoing intracavity reactions should be kept under the vapor of the diene.
54. Storm, D. R.; Koshland, D. E., Jr. J. Am. Chem. Soc. 1972, 94, 5805-5814.
55. uncat/[3], where [3] ≅ 10 M for the 1:20 mixture of dienophile 2a or 2b and diene 3.
56. (a) Kagan, B. F.; Riant, O. Chem. Rev. 1992, 92, 1007-1019.
57. (b) Pindur, U.; Luiz, G.; Otto, C. Ibid. 1993, 93, 741-761.
58. vc≡o for acrolein upon adduct formation.
59. There are numerous examples of facilitated solid-state reactions via hydrogen bonding (reference 1 ). For the effect of hydrogen bonding on the tautomeric composition, see: Herbstein, F. H.; Kapon, M.; Reisner, G. M.; Lehman, M. S.; Kress, R. B.; Wilson, R. B.; Shiau, W. I.; Duesler, E. N.; Paul, I. C.; Curtin, D. Y. Proc. R. Soc London 1985, A399, 295-319.
60. The size-insensitivity of the desorption properties might be interpreted as suggesting that the biphasic nature is due to some kind of phase transition in the crystal structure upon guest desorption or exchange and not due to its dependence on the depth of the cavity from the surface.
61. The mechanism of guest-exchange has not yet been established. It may even involve local dissolution of the host followed by its recrystallization. For related work, see references 5f and 8b.
62. -1.
63. For examples of templated bimolecular or multimolecular reactions, see: (a) Diederich, F.; Lutter, H.-D. J. Am. Chem. Soc. 1989, 111, 8438-8446. (b) Anderson, S.; Anderson, H.-L.; Sanders, J. K. M. Acc. Chem. Res. 1993, 26, 469-475. (c) Kelly, T. R.; Bridger, G. J.; Zhao, C. J. Am. Chem. Soc. 1990, 112, 8024-8034. (d) Nowick, J. S.; Feng, O.; Tjirijua, P.; Ballester, P.; Rebek, J., Jr. Ibid. 1991, 113, 8831-8839.
64. For examples of templated bimolecular or multimolecular reactions, see: (a) Diederich, F.; Lutter, H.-D. J. Am. Chem. Soc. 1989, 111, 8438-8446. (b) Anderson, S.; Anderson, H.-L.; Sanders, J. K. M. Acc. Chem. Res. 1993, 26, 469-475. (c) Kelly, T. R.; Bridger, G. J.; Zhao, C. J. Am. Chem. Soc. 1990, 112, 8024-8034. (d) Nowick, J. S.; Feng, O.; Tjirijua, P.; Ballester, P.; Rebek, J., Jr. Ibid. 1991, 113, 8831-8839.
65. For examples of templated bimolecular or multimolecular reactions, see: (a) Diederich, F.; Lutter, H.-D. J. Am. Chem. Soc. 1989, 111, 8438-8446. (b) Anderson, S.; Anderson, H.-L.; Sanders, J. K. M. Acc. Chem. Res. 1993, 26, 469-475. (c) Kelly, T. R.; Bridger, G. J.; Zhao, C. J. Am. Chem. Soc. 1990, 112, 8024-8034. (d) Nowick, J. S.; Feng, O.; Tjirijua, P.; Ballester, P.; Rebek, J., Jr. Ibid. 1991, 113, 8831-8839.
66. For examples of templated bimolecular or multimolecular reactions, see: (a) Diederich, F.; Lutter, H.-D. J. Am. Chem. Soc. 1989, 111, 8438-8446. (b) Anderson, S.; Anderson, H.-L.; Sanders, J. K. M. Acc. Chem. Res. 1993, 26, 469-475. (c) Kelly, T. R.; Bridger, G. J.; Zhao, C. J. Am. Chem. Soc. 1990, 112, 8024-8034. (d) Nowick, J. S.; Feng, O.; Tjirijua, P.; Ballester, P.; Rebek, J., Jr. Ibid. 1991, 113, 8831-8839.
67. For the enzymes catalyzing the Diels-Alder reactions, see: Oikawa, H.; Katayama, K.; Suzuki, Y.; Ichihara, A. J. Chem. Soc., Chem. Commun. 1995, 1321-1322. For the catalytic antibodies for the Diels - Alder reactions, see: (a) Hilvert, D.; Hill, K. W.; Nared, K. D.; Auditon, M.-J. M. J. Am. Chem. Soc. 1989, 111, 9261-9262. (b) Braisted, A. C.; Schultz, P. G. Ibid. 1990, 112, 7430-7431.
68. For the enzymes catalyzing the Diels-Alder reactions, see: Oikawa, H.; Katayama, K.; Suzuki, Y.; Ichihara, A. J. Chem. Soc., Chem. Commun. 1995, 1321-1322. For the catalytic antibodies for the Diels - Alder reactions, see: (a) Hilvert, D.; Hill, K. W.; Nared, K. D.; Auditon, M.-J. M. J. Am. Chem. Soc. 1989, 111, 9261-9262. (b) Braisted, A. C.; Schultz, P. G. Ibid. 1990, 112, 7430-7431.
69. For the enzymes catalyzing the Diels-Alder reactions, see: Oikawa, H.; Katayama, K.; Suzuki, Y.; Ichihara, A. J. Chem. Soc., Chem. Commun. 1995, 1321-1322. For the catalytic antibodies for the Diels - Alder reactions, see: (a) Hilvert, D.; Hill, K. W.; Nared, K. D.; Auditon, M.-J. M. J. Am. Chem. Soc. 1989, 111, 9261-9262. (b) Braisted, A. C.; Schultz, P. G. Ibid. 1990, 112, 7430-7431.
70. Cf., Mackay, L. G.; Wylie, R. S.; Sanders, J. K. M. J. Am. Chem. Soc. 1994, 116, 3141-3142.
71. When dipped in an aqueous solution of an appropriate guest such as cyclohexanol, cyclohexanediol, and alkyl acetate, apohost 1 binds two molecules of the guest together with 3-5 molecules of water (Aoyama, Y.; Imai, Y.; Endo, K.; Kobayashi, K. Tetrahedron 1995, 51, 343-352). The guest-binding turns out to be reversible. For example, exchange between ethyl acetate and propyl acetate readily takes place when the ethyl acetate adduct is dipped in an aqueous solution of propyl acetate (Aoyama, Y.; Oue, Y.; Sawaki, T.; Endo, K. unpublished results).
72. When dipped in an aqueous solution of an appropriate guest such as cyclohexanol, cyclohexanediol, and alkyl acetate, apohost 1 binds two molecules of the guest together with 3-5 molecules of water (Aoyama, Y.; Imai, Y.; Endo, K.; Kobayashi, K. Tetrahedron 1995, 51, 343-352). The guest-binding turns out to be reversible. For example, exchange between ethyl acetate and propyl acetate readily takes place when the ethyl acetate adduct is dipped in an aqueous solution of propyl acetate (Aoyama, Y.; Oue, Y.; Sawaki, T.; Endo, K. unpublished results).