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Acceleration of a Diels–Alder reaction by a self-assembled molecular capsule

Abstract

THE interior of cage-like molecules can be considered to provide a new phase of matter1,2, in which it becomes possible to stabilize reactive intermediates3 and to observe new forms of stereoisomerism4. Cage-like molecular complexes that self-assemble through weak intermolecular forces are dynamic species5,6, encapsulating guest molecules reversibly. They can persist over timescales ranging from microseconds to hours, long enough for chemical processes to take place within them. Here we report the acceleration of a Diels–Alder reaction by encapsulation of the reac-tants in a self-assembling molecular capsule7,8. Although product inhibition (lack of dissociation) prevents the system from showing true catalytic behaviour, there is clear evidence for a rate increase of over two orders of magnitude owing to the effective enhancement of concentration inside the capsule.

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References

  1. Sherman, J. C. & Cram, D. J. J. Am. Chem. Soc. 117, 4527–4528 (1989).

    Article  Google Scholar 

  2. Garel, L., Dutasta, J. -P. & Collet, A. Angew. Chem. Int. Edn Engl. 32, 1169–1171 (1993).

    Article  Google Scholar 

  3. Cram, D. J., Tanner, M. E. & Thomas, R. Angew. Chem. Int. Edn Engl. 30, 1024–1027 (1991).

    Article  Google Scholar 

  4. Timmerman, P., Verboom, W., van Veggel, F. C. J. M., van Duynhoven J. P. M. & Reinhoudt, D. N. Angew. Chem. Int. Edn Engl. 33, 2345–2348 (1994).

    Article  Google Scholar 

  5. Wyler, R., de Mendoza, J. & Rebek, J. Jr Angew. Chem. Int. Edn Engl. 32, 1699–1701 (1993).

    Article  Google Scholar 

  6. Valdés, C., Spitz, U. P., Toledo, L., Kubik, S. & Rebek, J. Jr J. Am. Chem. Soc. 117, 12733–12745 (1995).

    Article  Google Scholar 

  7. Meissner, R. S., de Mendoza, J. & Rebek, J. Jr Science 270, 1485–1488 (1995).

    Article  ADS  CAS  Google Scholar 

  8. Kang, J. & Rebek, J. Jr Nature 382, 239–241 (1996).

    Article  ADS  CAS  Google Scholar 

  9. Kelly, T. R., Meghani, P. & Ekkundi, V. S. Tetrahed. Lett. 31, 3381–3384 (1990).

    Article  CAS  Google Scholar 

  10. Meissner, R., Garcias, X., Mecozzi, S. & Rebek, J. Jr J. Am. Chem. Soc. (in the press).

  11. Kirby, A. J. Adv. Phys. Org. Chem. 17, 183–278 (1980).

    CAS  Google Scholar 

  12. Mock, W. L., Irra, T. A., Wepsiec, J. P. & Adhya, M. J. Org. Chem. 54, 5302–5308 (1989).

    Article  CAS  Google Scholar 

  13. McCurdy, A., Jimenez, L., Stauffer, D. A. & Dougherty, D. A. J. Am. Chem. Soc. 114, 10314–10321 (1992).

    Article  CAS  Google Scholar 

  14. Hilvert, D., Hill, K. W. & Auditor, M. T. M. J. Am. Chem. Soc. 111, 9261–9263 (1989).

    Article  CAS  Google Scholar 

  15. Grieco, P. A., Garner, P. & He, Z.-M. Tetrahedr. Lett. 24, 1897–1900 (1983).

    Article  CAS  Google Scholar 

  16. Breslow, R., Maitra, U. & Rideout, D. Tetrahedr. Lett. 24, 1901–1904 (1983).

    Article  CAS  Google Scholar 

  17. Braun, R., Schuster, F. & Sauer, J. Tetrahedr. Lett. 27, 1285–1288 (1986).

    Article  CAS  Google Scholar 

  18. Singh, V. K., Raju, B. N. S. & Deota, P. T. Synth. Commun. 18, 567–574 (1988).

    Article  CAS  Google Scholar 

  19. Grieco, P. A., Kaufman, M. D., Daeuble, J. F. & Saito, N. J. Am. Chem. Soc. 118, 2095–2096 (1996).

    Article  CAS  Google Scholar 

  20. Breslow, R. & Guo, T. J. Am. Chem. Soc. 110, 5613–5617 (1988).

    Article  CAS  Google Scholar 

  21. Walter, C. J., Anderson, H. L. & Sanders, J. K. M. J. Chem. Soc. Chem. Commun. 459–460 (1993).

  22. Mohamadi, F. et al. J. Comput. Chem. 11, 440–467 (1990).

    Article  CAS  Google Scholar 

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Kang, J., Rebek, J. Acceleration of a Diels–Alder reaction by a self-assembled molecular capsule. Nature 385, 50–52 (1997). https://doi.org/10.1038/385050a0

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