Solvent effects on Diels-Alder reactions. The use of aqueous mixtures of fluorinated alcohols and the study of reactions of acrylonitrile

(Note: The full text of this document is currently only available in the PDF Version )

Carlos Cativiela, Jose I. García, J. Gil, Rosa M. Martínez, Jose A. Mayoral, Luis Salvatella, Jose S. Urieta, A. M. Mainar and Michael H. Abraham


Abstract

Rate, endo/exo, regio- and diastereo-facial selectivities of several Diels–Alder reactions were measured in a series of fluorinated alcohol–water mixtures, whose solvophobicity has been determined by means of the solvophobic power (Sp) parameter. Solvophobicity is the main factor influencing the reaction rate, although in some reactions hydrogen bond donating (HBD) ability may also play a role. Both solvophobicity and HBD ability are important to account for changes in endo/exo selectivity. HBD ability is the main factor responsible for the changes in regio- and diastereo-facial selectivities, induced by the reaction medium. On the other hand, the kinetic rate constants and endo/exo selectivity of the reaction of acrylonitrile with cyclopentadiene, as well as the regioselectivity of the reaction of acrylonitrile with isoprene, have been determined in 23 reaction media. The analysis of the results using empirical solvent parameters show that the reaction rate depends on solvophobic, HBD and dipolarity interactions, whereas endo/exo selectivity is influenced by solvophobic and dipolarity interactions, and the regioselectivity only by HBD effects.


References

  1. C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, VCH, Weinheim, 1988 Search PubMed.
  2. C. Cativiela, J. I. García, J. A. Mayoral and L. Salvatella, Chem. Soc. Rev., 1996, 209 Search PubMed.
  3. (a) H.-J. Schneider and N. K. Sangwan, J. Chem. Soc., Chem. Commun., 1986, 1781 Search PubMed; (b) N. K. Sangwan and H.-J. Schneider, J. Chem. Soc., Perkin Trans. 2, 1989, 1223 Search PubMed; (c) C. Cativiela, J. A. Mayoral, A. Avenoza, J. M. Peregrina and M. A. Roy, J. Phys. Org. Chem., 1990, 3, 414 Search PubMed.
  4. C. Cativiela, J. I. García, J. A. Mayoral, A. Avenoza, J. M. Peregrina and M. A. Roy, J. Phys. Org. Chem., 1991, 4, 48 Search PubMed.
  5. C. Cativiela, J. I. García, J. A. Mayoral, A. J. Royo, L. Salvatella, X. Assfeld and M. F. Ruiz-López, J. Phys. Org. Chem., 1992, 5, 230 Search PubMed.
  6. C. Cativiela, J. I. García, J. A. Mayoral, A. J. Royo and L. Salvatella, Tetrahedron:Asymmetry, 1993, 4, 1613 Search PubMed.
  7. C. Cativiela, J. I. García, J. A. Mayoral and L. Salvatella, Can. J. Chem., 1994, 72, 308 Search PubMed.
  8. H.-J. Schneider and N. K. Sangwan, Angew. Chem., Int. Ed. Engl., 1987, 26, 896 Search PubMed.
  9. C. Cativiela, J. I. García, J. A. Mayoral and L. Salvatella, J. Chem. Soc., Perkin Trans. 2, 1994, 847 Search PubMed.
  10. M. H. Abraham, P. L. Grellier and R. A. McGill, J Chem. Soc., Perkin Trans. 2, 1988, 339 Search PubMed.
  11. C. Cativiela, V. Dillet, J. I. García, J. A. Mayoral, M. F. Ruiz-López and L. Salvatella, J. Mol. Struct. (THEOCHEM), 1995, 331, 37 Search PubMed.
  12. D. C. Rideout and R. Breslow, J. Am. Chem. Soc., 1980, 102, 7816 Search PubMed.
  13. J. F. Blake, D. Lim and W. L. Jorgensen, J. Org. Chem., 1994, 59, 803 Search PubMed.
  14. T. Asano and W. J. Le Noble, Chem. Rev., 1978, 78, 407 Search PubMed.
  15. T. Karcher, W. Sicking, J. Sauer and R. Sustmann, Tetrahedron Lett., 1992, 33, 8027 Search PubMed.
  16. V. D. Kiselev and A. I. Konovalov, Usp. Khim., 1989, 58, 383 Search PubMed; Russ. Chem. Rev., 1989, 58, 230 Search PubMed.
  17. J. C. Soula, D. Lumbroso, M. Hellin and F. Coussemant, Bull. Soc. Chim. Fr., 1966, 2065 Search PubMed.
  18. A. Ben-Naim and S. Baer, Trans. Faraday Soc., 1963, 59, 2735 Search PubMed.
  19. F. Gibanel, M. C. López, F. Royo, V. Rodríguez and J. S. Urieta, J. Solution Chem., 1994, 23, 1061 Search PubMed.
  20. S. Bo, R. Battino and E. Wilhelm, J. Chem. Eng. Data, 1993, 38, 611 Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.