Chiral microenvironments in self-assembled capsules

Journal of the American Chemical Society

Volumn 121, Issue 44, 1999, Pages 10281-10285

  Nuckolls, Colin ^a   Hof, Fraser ^a   Martín, Tomás ^a   Rebek Jr , Julius ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

TETRAMER;

ARTICLE; CHIRALITY; ENANTIOMER; ENCAPSULATION; HYDROGEN BOND; SYNTHESIS;

EID: 0033544412     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992779m     Document Type: Article

References (26)

1. Structures that self-assemble into discreet, nonracemic assemblies are known but their superstructures leave little room for guests. Hydrogenbonded: (a) Simanek, E. E.; Qiao, S.; Choi, I. S.; Whitesides, G. M. J. Org. Chem. 1997, 62, 2619. (b) Sanchez-Quesada, J.; Seel, C.; Prados, P.; de Mendoza, J.; Dalcol, I.; Giralt, E. J. Am. Chem. Soc. 1996, 118, 277. (c) Prins, L. J.; Huskens, J.; de Jong, F.; Timmerman, P.; Reinhoudt, D. N. Nature 1999, 398, 498. Metal-based: (d) Zarges, W.; Hall, J.; Lehn, J. M.; Bolm, C. Helv. Chim. Acta 1991, 74, 1843 and references therein. (e) Enemark, E. J.; Stack, D. T. P. Angew. Chem., Int. Ed. Engl. 1998, 37, 932. (f) Case, M. A.; Ghadiri, M. R.; Mutz, M. W.; McLendon, G. L. Chirality 1998, 10, 35. Rrotaxanes/catenanes: (g) Asakawa, M.; Janssen, H. M.; Meijer, E. W.; Pasini, D.; Stoddart, J. F. Eur. J. Org. Chem. 1998, 6, 983 and references therein.
2. Structures that self-assemble into discreet, nonracemic assemblies are known but their superstructures leave little room for guests. Hydrogenbonded: (a) Simanek, E. E.; Qiao, S.; Choi, I. S.; Whitesides, G. M. J. Org. Chem. 1997, 62, 2619. (b) Sanchez-Quesada, J.; Seel, C.; Prados, P.; de Mendoza, J.; Dalcol, I.; Giralt, E. J. Am. Chem. Soc. 1996, 118, 277. (c) Prins, L. J.; Huskens, J.; de Jong, F.; Timmerman, P.; Reinhoudt, D. N. Nature 1999, 398, 498. Metal-based: (d) Zarges, W.; Hall, J.; Lehn, J. M.; Bolm, C. Helv. Chim. Acta 1991, 74, 1843 and references therein. (e) Enemark, E. J.; Stack, D. T. P. Angew. Chem., Int. Ed. Engl. 1998, 37, 932. (f) Case, M. A.; Ghadiri, M. R.; Mutz, M. W.; McLendon, G. L. Chirality 1998, 10, 35. Rrotaxanes/catenanes: (g) Asakawa, M.; Janssen, H. M.; Meijer, E. W.; Pasini, D.; Stoddart, J. F. Eur. J. Org. Chem. 1998, 6, 983 and references therein.
3. Structures that self-assemble into discreet, nonracemic assemblies are known but their superstructures leave little room for guests. Hydrogenbonded: (a) Simanek, E. E.; Qiao, S.; Choi, I. S.; Whitesides, G. M. J. Org. Chem. 1997, 62, 2619. (b) Sanchez-Quesada, J.; Seel, C.; Prados, P.; de Mendoza, J.; Dalcol, I.; Giralt, E. J. Am. Chem. Soc. 1996, 118, 277. (c) Prins, L. J.; Huskens, J.; de Jong, F.; Timmerman, P.; Reinhoudt, D. N. Nature 1999, 398, 498. Metal-based: (d) Zarges, W.; Hall, J.; Lehn, J. M.; Bolm, C. Helv. Chim. Acta 1991, 74, 1843 and references therein. (e) Enemark, E. J.; Stack, D. T. P. Angew. Chem., Int. Ed. Engl. 1998, 37, 932. (f) Case, M. A.; Ghadiri, M. R.; Mutz, M. W.; McLendon, G. L. Chirality 1998, 10, 35. Rrotaxanes/catenanes: (g) Asakawa, M.; Janssen, H. M.; Meijer, E. W.; Pasini, D.; Stoddart, J. F. Eur. J. Org. Chem. 1998, 6, 983 and references therein.
4. Structures that self-assemble into discreet, nonracemic assemblies are known but their superstructures leave little room for guests. Hydrogenbonded: (a) Simanek, E. E.; Qiao, S.; Choi, I. S.; Whitesides, G. M. J. Org. Chem. 1997, 62, 2619. (b) Sanchez-Quesada, J.; Seel, C.; Prados, P.; de Mendoza, J.; Dalcol, I.; Giralt, E. J. Am. Chem. Soc. 1996, 118, 277. (c) Prins, L. J.; Huskens, J.; de Jong, F.; Timmerman, P.; Reinhoudt, D. N. Nature 1999, 398, 498. Metal-based: (d) Zarges, W.; Hall, J.; Lehn, J. M.; Bolm, C. Helv. Chim. Acta 1991, 74, 1843 and references therein. (e) Enemark, E. J.; Stack, D. T. P. Angew. Chem., Int. Ed. Engl. 1998, 37, 932. (f) Case, M. A.; Ghadiri, M. R.; Mutz, M. W.; McLendon, G. L. Chirality 1998, 10, 35. Rrotaxanes/catenanes: (g) Asakawa, M.; Janssen, H. M.; Meijer, E. W.; Pasini, D.; Stoddart, J. F. Eur. J. Org. Chem. 1998, 6, 983 and references therein.
5. Structures that self-assemble into discreet, nonracemic assemblies are known but their superstructures leave little room for guests. Hydrogenbonded: (a) Simanek, E. E.; Qiao, S.; Choi, I. S.; Whitesides, G. M. J. Org. Chem. 1997, 62, 2619. (b) Sanchez-Quesada, J.; Seel, C.; Prados, P.; de Mendoza, J.; Dalcol, I.; Giralt, E. J. Am. Chem. Soc. 1996, 118, 277. (c) Prins, L. J.; Huskens, J.; de Jong, F.; Timmerman, P.; Reinhoudt, D. N. Nature 1999, 398, 498. Metal-based: (d) Zarges, W.; Hall, J.; Lehn, J. M.; Bolm, C. Helv. Chim. Acta 1991, 74, 1843 and references therein. (e) Enemark, E. J.; Stack, D. T. P. Angew. Chem., Int. Ed. Engl. 1998, 37, 932. (f) Case, M. A.; Ghadiri, M. R.; Mutz, M. W.; McLendon, G. L. Chirality 1998, 10, 35. Rrotaxanes/catenanes: (g) Asakawa, M.; Janssen, H. M.; Meijer, E. W.; Pasini, D.; Stoddart, J. F. Eur. J. Org. Chem. 1998, 6, 983 and references therein.
6. Structures that self-assemble into discreet, nonracemic assemblies are known but their superstructures leave little room for guests. Hydrogenbonded: (a) Simanek, E. E.; Qiao, S.; Choi, I. S.; Whitesides, G. M. J. Org. Chem. 1997, 62, 2619. (b) Sanchez-Quesada, J.; Seel, C.; Prados, P.; de Mendoza, J.; Dalcol, I.; Giralt, E. J. Am. Chem. Soc. 1996, 118, 277. (c) Prins, L. J.; Huskens, J.; de Jong, F.; Timmerman, P.; Reinhoudt, D. N. Nature 1999, 398, 498. Metal-based: (d) Zarges, W.; Hall, J.; Lehn, J. M.; Bolm, C. Helv. Chim. Acta 1991, 74, 1843 and references therein. (e) Enemark, E. J.; Stack, D. T. P. Angew. Chem., Int. Ed. Engl. 1998, 37, 932. (f) Case, M. A.; Ghadiri, M. R.; Mutz, M. W.; McLendon, G. L. Chirality 1998, 10, 35. Rrotaxanes/catenanes: (g) Asakawa, M.; Janssen, H. M.; Meijer, E. W.; Pasini, D.; Stoddart, J. F. Eur. J. Org. Chem. 1998, 6, 983 and references therein.
7. Structures that self-assemble into discreet, nonracemic assemblies are known but their superstructures leave little room for guests. Hydrogenbonded: (a) Simanek, E. E.; Qiao, S.; Choi, I. S.; Whitesides, G. M. J. Org. Chem. 1997, 62, 2619. (b) Sanchez-Quesada, J.; Seel, C.; Prados, P.; de Mendoza, J.; Dalcol, I.; Giralt, E. J. Am. Chem. Soc. 1996, 118, 277. (c) Prins, L. J.; Huskens, J.; de Jong, F.; Timmerman, P.; Reinhoudt, D. N. Nature 1999, 398, 498. Metal-based: (d) Zarges, W.; Hall, J.; Lehn, J. M.; Bolm, C. Helv. Chim. Acta 1991, 74, 1843 and references therein. (e) Enemark, E. J.; Stack, D. T. P. Angew. Chem., Int. Ed. Engl. 1998, 37, 932. (f) Case, M. A.; Ghadiri, M. R.; Mutz, M. W.; McLendon, G. L. Chirality 1998, 10, 35. Rrotaxanes/catenanes: (g) Asakawa, M.; Janssen, H. M.; Meijer, E. W.; Pasini, D.; Stoddart, J. F. Eur. J. Org. Chem. 1998, 6, 983 and references therein.
8. Nonracemic structures whose peripherally located chirality does not translate to significant enantioselective recognition: (a) Tokunaga, Y.; Rebek, J., Jr. J. Am. Chem. Soc. 1998, 120, 66. (b) Castellano, R. K.; Kim, B. H.; Rebek, J., Jr. J. Am. Chem. Soc. 1997, 119, 12671. (c) Mueller, C.; Whiteford, J. A.; Stang, P. J. J. Am. Chem. Soc. 1998, 120, 9827.
9. Nonracemic structures whose peripherally located chirality does not translate to significant enantioselective recognition: (a) Tokunaga, Y.; Rebek, J., Jr. J. Am. Chem. Soc. 1998, 120, 66. (b) Castellano, R. K.; Kim, B. H.; Rebek, J., Jr. J. Am. Chem. Soc. 1997, 119, 12671. (c) Mueller, C.; Whiteford, J. A.; Stang, P. J. J. Am. Chem. Soc. 1998, 120, 9827.
10. Nonracemic structures whose peripherally located chirality does not translate to significant enantioselective recognition: (a) Tokunaga, Y.; Rebek, J., Jr. J. Am. Chem. Soc. 1998, 120, 66. (b) Castellano, R. K.; Kim, B. H.; Rebek, J., Jr. J. Am. Chem. Soc. 1997, 119, 12671. (c) Mueller, C.; Whiteford, J. A.; Stang, P. J. J. Am. Chem. Soc. 1998, 120, 9827.
11. (a) Conn, M. M.; Rebek, J., Jr. Chem. Rev. 1997, 97, 1647.
12. (b) Rebek, J., Jr. Acc. Chem. Res. 1999, 32, 278.
13. Rivera, J. M.; Martín, T.; Rebek, J., Jr. Science 1998, 279, 1041. Rivera, J. M.; Martín, T.; Rebek, J., Jr. Science 1998, 279, 1041.
14. Rivera, J. M.; Martín, T.; Rebek, J., Jr. Science 1998, 279, 1041. Rivera, J. M.; Martín, T.; Rebek, J., Jr. Science 1998, 279, 1041.
15. Martín, T.; Obst, U.; Rebek, J., Jr. Science 1998, 281, 1842.
16. All molecular modeling was performed with MacroModel 6.5 and the structures were energy minimized with the Amber* force field: Mohamadi, F.; Richards, N. G. J.; Guida, W. C.; Liskamp, R.; Lipton, M.; Caufield, C.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440. The volumes of the cavities were calculated for these structures by using the GRASP program: Nicholls, A.; Sharp, K. A.; Honig, B. Proteins 1991, 11, 281.
17. All molecular modeling was performed with MacroModel 6.5 and the structures were energy minimized with the Amber* force field: Mohamadi, F.; Richards, N. G. J.; Guida, W. C.; Liskamp, R.; Lipton, M.; Caufield, C.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440. The volumes of the cavities were calculated for these structures by using the GRASP program: Nicholls, A.; Sharp, K. A.; Honig, B. Proteins 1991, 11, 281.
18. Phenols have been shown to increase the encapsulating power of other hydrogen-bonded capsules in a similar fashion: Kang, J.; Hilmersson, G.; Santamaría, J.; Rebek, J., Jr. J. Am. Chem. Soc. 1998, 120, 3650.
19. Tracy, M.; Acton, E. M. J. Org. Chem. 1984, 49, 5116.
20. Synthesized by the procedure given by: Moral, C.; Rassat, A. Tetrahedron Lett. 1979, 45, 4409.
21. This guest was shown to have the highest binding constant in the original tetrameric assembly (see ref 5).
22. Breaking of the end-to-end symmetry is accompanied by rotation of the guest that must be slow on the NMR time scale. This type of hindered rotation of guests has been observed for other encapsulated molecules: (a) See ref 2b. (b) Chapman, R. G.; Sherman, J. C. J. Am. Chem. Soc. 1995, 117, 9081.
23. Breaking of the end-to-end symmetry is accompanied by rotation of the guest that must be slow on the NMR time scale. This type of hindered rotation of guests has been observed for other encapsulated molecules: (a) See ref 2b. (b) Chapman, R. G.; Sherman, J. C. J. Am. Chem. Soc. 1995, 117, 9081.
24. [2.2.1]-Bicycloheptane-2,5-dione is prepared by the procedure given by: Hawkins, R. T.; Hsu, R. S.; Wood, S. G. J. Org. Chem. 1978, 43, 4648. [2.2.2]-Bicyclooctane-2,5-dione is prepared by the procedure given by: Werstiuk, N. H.; Yeroushalmi, S.; Hong, G. L. Can. J. Chem. 1992, 70, 974.
25. [2.2.1]-Bicycloheptane-2,5-dione is prepared by the procedure given by: Hawkins, R. T.; Hsu, R. S.; Wood, S. G. J. Org. Chem. 1978, 43, 4648. [2.2.2]-Bicyclooctane-2,5-dione is prepared by the procedure given by: Werstiuk, N. H.; Yeroushalmi, S.; Hong, G. L. Can. J. Chem. 1992, 70, 974.
26. Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518-1520.