An Unexpected Rate Acceleration-Practical Improvements in the Baylis-Hillman Reaction

Journal of Organic Chemistry

Volumn 62, Issue 5, 1997, Pages 1521-1522

  Rafel, Sara ^a   Leahy, James W ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0345863483     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961224w     Document Type: Article

References (25)

1. For a review of recent trends in organic synthesis, see: Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991.
2. For reviews of the Baylis-Hillman reaction, see: (a) Basavaiah, D.; Rao, P. D.; Hyma, R. S. Tetrahedron 1996, 52, 8001. (b) Drewes, S. E.; Roos, G. H. P. Tetrahedron 1988, 44, 4653. See also: Morita, K.; Suzuki, Z.; Hirose, H. Bull. Chem. Soc. Jpn. 1968, 41, 2815.
3. For reviews of the Baylis-Hillman reaction, see: (a) Basavaiah, D.; Rao, P. D.; Hyma, R. S. Tetrahedron 1996, 52, 8001. (b) Drewes, S. E.; Roos, G. H. P. Tetrahedron 1988, 44, 4653. See also: Morita, K.; Suzuki, Z.; Hirose, H. Bull. Chem. Soc. Jpn. 1968, 41, 2815.
4. For reviews of the Baylis-Hillman reaction, see: (a) Basavaiah, D.; Rao, P. D.; Hyma, R. S. Tetrahedron 1996, 52, 8001. (b) Drewes, S. E.; Roos, G. H. P. Tetrahedron 1988, 44, 4653. See also: Morita, K.; Suzuki, Z.; Hirose, H. Bull. Chem. Soc. Jpn. 1968, 41, 2815.
5. For examples, see: (a) Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993, 93, 1307. (b) Atkinson, R. S.; Fawcett, J.; Russell, D. R.; Williams, P. J. J. Chem. Soc., Chem. Commun. 1994, 2031. (c) Basaviah, D.; Bhavani, A. K. D.; Pandiaraju, S.; Sarma, P. K. S. Synlett 1995, 243. (d) Annunziata, R.; Benaglia, M.; Cinquini, M.; Cozzi, F.; Raimondi, L. J. Org. Chem. 1995, 60, 4697.
6. For examples, see: (a) Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993, 93, 1307. (b) Atkinson, R. S.; Fawcett, J.; Russell, D. R.; Williams, P. J. J. Chem. Soc., Chem. Commun. 1994, 2031. (c) Basaviah, D.; Bhavani, A. K. D.; Pandiaraju, S.; Sarma, P. K. S. Synlett 1995, 243. (d) Annunziata, R.; Benaglia, M.; Cinquini, M.; Cozzi, F.; Raimondi, L. J. Org. Chem. 1995, 60, 4697.
7. For examples, see: (a) Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993, 93, 1307. (b) Atkinson, R. S.; Fawcett, J.; Russell, D. R.; Williams, P. J. J. Chem. Soc., Chem. Commun. 1994, 2031. (c) Basaviah, D.; Bhavani, A. K. D.; Pandiaraju, S.; Sarma, P. K. S. Synlett 1995, 243. (d) Annunziata, R.; Benaglia, M.; Cinquini, M.; Cozzi, F.; Raimondi, L. J. Org. Chem. 1995, 60, 4697.
8. For examples, see: (a) Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993, 93, 1307. (b) Atkinson, R. S.; Fawcett, J.; Russell, D. R.; Williams, P. J. J. Chem. Soc., Chem. Commun. 1994, 2031. (c) Basaviah, D.; Bhavani, A. K. D.; Pandiaraju, S.; Sarma, P. K. S. Synlett 1995, 243. (d) Annunziata, R.; Benaglia, M.; Cinquini, M.; Cozzi, F.; Raimondi, L. J. Org. Chem. 1995, 60, 4697.
9. See, for example: Roush, W. R.; Brown, B. B. J. Org. Chem. 1993, 58, 2151.
10. Jenn, T.; Heissler, D. Synlett 1995, 607.
11. Fort, Y.; Berthe, M. C.; Caubere, P. Tetrahedron 1992, 48, 6371.
12. Augé, J.; Lubin, N.; Lubineau, A. Tetrahedron Lett. 1994, 35, 7947. Kundu, M. K.; Mukherjee, S. B.; Balu, N.; Padmakumar, R.; Bhat, S. V. Synlett 1994, 444. Hill, J. S.; Isaacs, N. S. J. Chem. Res., Synop. 1988, 330.
13. Augé, J.; Lubin, N.; Lubineau, A. Tetrahedron Lett. 1994, 35, 7947. Kundu, M. K.; Mukherjee, S. B.; Balu, N.; Padmakumar, R.; Bhat, S. V. Synlett 1994, 444. Hill, J. S.; Isaacs, N. S. J. Chem. Res., Synop. 1988, 330.
14. Augé, J.; Lubin, N.; Lubineau, A. Tetrahedron Lett. 1994, 35, 7947. Kundu, M. K.; Mukherjee, S. B.; Balu, N.; Padmakumar, R.; Bhat, S. V. Synlett 1994, 444. Hill, J. S.; Isaacs, N. S. J. Chem. Res., Synop. 1988, 330.
15. Brzezinski, L. J.; Rafel, S.; Leahy, J. W. J. Am. Chem. Soc. Submitted.
16. Reaction of isobutyraldehyde with methyl acrylate under amine-catalyzed Baylis-Hillman conditions (eq i) leads to a mixture of products containing largely the self-aldol product 4 as opposed to 3f (Brzezinski, L. J. Unpublished results). Equation Presented
17. The use of tributylphosphine as a catalyst has been reported previously. See: Miyakoshi, T.; Omichi, H.; Saito, S. Nippon Kagaku Kaishi 1979, 748. See also: Chem. Abstr. 1979, 91, 123360d.
18. The use of tributylphosphine as a catalyst has been reported previously. See: Miyakoshi, T.; Omichi, H.; Saito, S. Nippon Kagaku Kaishi 1979, 748. See also: Chem. Abstr. 1979, 91, 123360d.
19. For the purposes of a direct comparison, the reaction of methyl acrylate and propionaldehyde was performed with DABCO for 2 days, and less than 10% of desired product 3e was obtained.
20. At elevated temperatures, the polymerization of the acrylate apparently becomes a viable alternative. The formation of this byproduct makes purification of the desired Baylis-Hillman adducts exceedingly difficult and should typically be avoided. Roos and Rampersadh have observed that "gentle warming" effects a marked rate increase in the reaction with acetaldehyde and a slight increase with other aldehydes (Roos, G. H. P.; Rampersadh, P. Synth. Commun. 1993, 23, 1261), but they also observed polymerization at temperatures above 43°C.
21. 17 and acrylonitrile is not capable of forming an ionically stabilized enolate such as a. Equation Presented
22. While the reaction with tributylphosphine at low temperature rapidly generates the desired products with rapid efficiency, the ease with which the catalytic DABCO is removed makes it the preferred catalyst from a practical viewpoint.
23. For example, see: Brzezinski, L. J.; Levy, D. D.; Leahy, J. W. Tetrahedron Lett. 1994, 35, 7601.
24. For general experimental conditions, see: Provencal, D. P.; Leahy, J. W. J. Org. Chem. 1994, 59, 5496.
25. Hill, J. S.; Isaacs, N. S. J. Chem. Res., Synop. 1988, 330.