Chiral space in a unimolecular capsule [1]

Journal of the American Chemical Society

Volumn 122, Issue 32, 2000, Pages 7811-7812

  Rivera, José M ^a   Rebek Jr , Julius ^a  

^a NONE

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CHEMICAL STRUCTURE; CHIRALITY; COVALENT BOND; DIASTEREOISOMER; DISSOCIATION; ENANTIOMER; HYDROGEN BOND; LETTER; POLYMERIZATION; STEREOCHEMISTRY;

EID: 0034675006     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0016304     Document Type: Letter

References (22)

1. For recent reviews on self-assembled capsules see: (a) Rebek, J., Jr. Acc. Chem. Res. 1999, 32, 278-286. (b) Conn, M. M.; Rebek, J., Jr. Chem. Rev. 1997, 97, 1647-1668.
2. For recent reviews on self-assembled capsules see: (a) Rebek, J., Jr. Acc. Chem. Res. 1999, 32, 278-286. (b) Conn, M. M.; Rebek, J., Jr. Chem. Rev. 1997, 97, 1647-1668.
3. (a) Rivera, J. M.; Martín, T.; Rebek, J., Jr. Science 1998, 279, 1021-1023.
4. For examples of other chiral nonracemic capsules, see: (b) Nuckolls, C.; Hof, F.; Martín, T.; Rebek, J., Jr. J. Am. Chem. Soc. 1999, 121, 10281-10285.
5. (c) Castellano, R. K.; Nuckolls, C.; Rebek, J., Jr. J. Am. Chem. Soc. 1999, 121, 11156-11163.
6. Rivera, J. M.; Craig, S. L.; Martín, T.; Rebek, J., Jr. Angew. Chem., Int. Ed. 2000, 39, 2130-3132.
7. For examples of covalent-based chiral capsules see: (a) Park, B. S.; Knobler, C. B.; Eid, C. N., Jr.; Warmuth, R.; Cram, D. J. Chem. Commun. 1998, 55-56. (b) Costante-Crassous, J.; Marrone, T. J.; Briggs, J. M.; McCammon, J. A.; Collet, A. J. Am. Chem. Soc. 1997, 119, 3818-3823. (c) Yoon, J.; Cram, D. J. J. Am. Chem. Soc. 1997, 119, 11796-11806. (d) Judice, J. K.; Cram, D. J. J. Am. Chem. Soc. 1991, 113, 2790-2791. (e) Collet, A. Tetrahedron 1987, 43, 5725-5759.
8. For examples of covalent-based chiral capsules see: (a) Park, B. S.; Knobler, C. B.; Eid, C. N., Jr.; Warmuth, R.; Cram, D. J. Chem. Commun. 1998, 55-56. (b) Costante-Crassous, J.; Marrone, T. J.; Briggs, J. M.; McCammon, J. A.; Collet, A. J. Am. Chem. Soc. 1997, 119, 3818-3823. (c) Yoon, J.; Cram, D. J. J. Am. Chem. Soc. 1997, 119, 11796-11806. (d) Judice, J. K.; Cram, D. J. J. Am. Chem. Soc. 1991, 113, 2790-2791. (e) Collet, A. Tetrahedron 1987, 43, 5725-5759.
9. For examples of covalent-based chiral capsules see: (a) Park, B. S.; Knobler, C. B.; Eid, C. N., Jr.; Warmuth, R.; Cram, D. J. Chem. Commun. 1998, 55-56. (b) Costante-Crassous, J.; Marrone, T. J.; Briggs, J. M.; McCammon, J. A.; Collet, A. J. Am. Chem. Soc. 1997, 119, 3818-3823. (c) Yoon, J.; Cram, D. J. J. Am. Chem. Soc. 1997, 119, 11796-11806. (d) Judice, J. K.; Cram, D. J. J. Am. Chem. Soc. 1991, 113, 2790-2791. (e) Collet, A. Tetrahedron 1987, 43, 5725-5759.
10. For examples of covalent-based chiral capsules see: (a) Park, B. S.; Knobler, C. B.; Eid, C. N., Jr.; Warmuth, R.; Cram, D. J. Chem. Commun. 1998, 55-56. (b) Costante-Crassous, J.; Marrone, T. J.; Briggs, J. M.; McCammon, J. A.; Collet, A. J. Am. Chem. Soc. 1997, 119, 3818-3823. (c) Yoon, J.; Cram, D. J. J. Am. Chem. Soc. 1997, 119, 11796-11806. (d) Judice, J. K.; Cram, D. J. J. Am. Chem. Soc. 1991, 113, 2790-2791. (e) Collet, A. Tetrahedron 1987, 43, 5725-5759.
11. For examples of covalent-based chiral capsules see: (a) Park, B. S.; Knobler, C. B.; Eid, C. N., Jr.; Warmuth, R.; Cram, D. J. Chem. Commun. 1998, 55-56. (b) Costante-Crassous, J.; Marrone, T. J.; Briggs, J. M.; McCammon, J. A.; Collet, A. J. Am. Chem. Soc. 1997, 119, 3818-3823. (c) Yoon, J.; Cram, D. J. J. Am. Chem. Soc. 1997, 119, 11796-11806. (d) Judice, J. K.; Cram, D. J. J. Am. Chem. Soc. 1991, 113, 2790-2791. (e) Collet, A. Tetrahedron 1987, 43, 5725-5759.
12. For other examples of self-assembly with covalent modifications see: Clark, T. D.; Kobayashi, K.; Ghadiri, M. R. Chem. Eur. J. 1999, 5, 782-792 and references therein.
13. Emde, H.; Götz, A.; Hofmann, K.; Simchen, G. Liebigs Ann. Chem. 1981, 1643-1657.
14. Reetz, M. T.; Neumeier, G. Chem. Ber. 1979, 112, 2209-2219.
15. Reddy, P. Y.; Kondo, S.; Toru, T.; Ueno, Y. J. Org. Chem. 1997, 62, 2652-2654.
16. Tokunaga, Y.; Rudkevich, D. M.; Santamaría, J.; Hilmersson, G.; Rebek, J., Jr. Chem. Eur. J. 1998, 4, 1449-1457.
17. Molecular modeling of capsules was carried out using MacroModel 6.5 and the Amber* force field: Mohamadi, F.; Richards, N. G.; Guida, W. C.; Liskamp, R.; Lipton, M.; Caufield, G.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440.
18. A compound similar to 14′, but with a flexible linker, showed the predominant formation of the closed conformation, although small amounts of other unidentified species were also present: Rivera, J. M. Ph.D. Thesis, Massachusetts Institute of Technology, 2000.
19. The R in aS-R describes the configuration of the chiral auxiliary used in the glycoluril. In the chiral softballs as well as in 14 the chirality of the cavity is determined primarily by the spacers used in the monomers (i.e., the phenyl ring and the ethylene spacers of 14). When the linker of the CLAM in Figure 1 is disregarded, there is a vertical chiral axis running through the middle of the capsule. A view down this chiral axis shows two "arms" pointing up and two pointing down. We classify the chiral cavities in these systems by using the length of the spacers to determine priorities. Near arms precede far arms and the longer arm gets the highest priority (1 and 3 respectively). If sense from 1 to 3 is clockwise, the configuration is aS (a for axial) or P.; if counterclockwise, the configuration is aR or M. For more on nomenclature of chiral compounds see: Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds; John Wiley & Sons: New York, 1994; pp 1119-1122.
20. (a) Kang, J.; Rebek, J., Jr. Nature 1997, 385, 50-52.
21. (b) Kang, J.; Santamaria, J.; Hilmersson, G.; Rebek, J., Jr. J. Am. Chem. Soc. 1998, 120, 3650-3656.
22. Brody, M. S.; Schalley, C. A.; Rudkevich, D. M.; Rebek, J., Jr. Angew. Chem., Int. Ed. 1999, 38, 1640-1644.