Acrylamide in the Baylis-Hillman reaction: Expanded reaction scope and the unexpected superiority of DABCO over more basic tertiary amine catalysts

Journal of Organic Chemistry

Volumn 69, Issue 19, 2004, Pages 6496-6499

  Faltin, Cornelia ^a   Fleming, Eimear M ^a   Connon, Stephen J ^a  

^a TRINITY COLLEGE DUBLIN   (Ireland)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOLS; ALDEHYDES; AMINES; AROMATIC COMPOUNDS; CATALYSTS; HYDROXYLATION; OPTIMIZATION; SOLVENTS; TERNARY SYSTEMS;

ACRYLAMIDES; AROMATIC ALDEHYDES; BAYLIS-HILLMAN REACTIONS; HYDROALKOXYLATION;

ACRYLICS;

1,4 DIAZABICYCLO[2.2.2]OCTANE; 4 METHYLBENZALDEHYDE; ACRYLAMIDE; ALCOHOL DERIVATIVE; ALDEHYDE DERIVATIVE; AMINE; ANISALDEHYDE; AROMATIC COMPOUND; QUINUCLIDINE; SOLVENT; UNCLASSIFIED DRUG;

AQUEOUS SOLUTION; ARTICLE; BAYLIS HILLMAN REACTION; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMICAL REACTION; MOLECULAR STABILITY; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; REPRODUCIBILITY; STOICHIOMETRY; TECHNIQUE; TEMPERATURE DEPENDENCE;

EID: 4644231912     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0490907     Document Type: Article

References (65)

1. Baylis, A. B.; Hillman M. E. D. Offenlegungsschrift 2155113, 1972; U.S. Patent 3,743,669; Chem. Abstr. 1972, 77, 34174q.
2. Reviews: (a) Basavaiah, D.; Rao, A. J.; Satyanarayana T. Chem. Rev. 2003, 103, 811.
3. (b) Iwabuchi, Y.; Hatakeyama, S. J. Synth. Org. Chem. Jpn. 2003, 60, 4.
4. (c) Langer, P. Angew. Chem., Int. Ed. 2000, 39, 3049.
5. (d) Ciganek, E. In Organic Reactions; Paquette, L. A., Ed.; Wiley: New York, 1997; Vol. 51, p 201.
6. (e) Basavaiah, D.; Dharma Rao, P.; Suguna Hyma, R. Tetrahedron 1996, 52, 8001.
7. (f) Drewes, S. E.; Roos, G. H. P. Tetrahedron 1988, 44, 4653.
8. (a) Ameer, F.; Drewes, S. E.; Freese, S.; Kaye, P. T. Synth. Commun. 1988, 18, 495.
9. (b) Drewes, S. E.; Freese, S. D.; Emslie, N. D.; Roos, G. H. P. Synth. Commun. 1988, 18, 1565.
10. (c) Markó, I. E.; Ollis, D. Rasmussen, P. R. Tetrahedron Lett. 1990, 31, 4509.
11. (d) Markó, I. E.; Giles, P. R.; Hindley, N. J. Tetrahedron 1997, 53, 1015.
12. (e) Barrett, A. G. M.; Cook, A. S.; Kamimura, A. Chem. Commun. 1998, 2533.
13. (f) Rezgui F.; El Gaied, M. M. Tetrahedron Lett. 1998, 39, 5965.
14. (g) Aggarwal, V. K.; Mereu, A. Chem. Commun. 1999, 2311.
15. (h) Leadbeater, N. E.; van der Pol, C. J. J. Chem. Soc., Perkin Trans. 1 2001, 2831.
16. (i) Octavio, R.; de Sousa, M. A.; Vasconcellos, M. L. A. A. Synth. Commun. 2003, 33, 1383
17. (j) Aggarwal, V. K.; Emme, I.; Fulford, S. Y. J. Org. Chem. 2003, 68, 692.
18. (k) Roth, F.; Gygax, P.; Frater, G. Tetrahedron Lett. 1992, 33, 1045.
19. (l) Li, W.; Zhang, Z.; Xiao, D.; Zhang, X. J. Org. Chem. 2000, 65, 3489.
20. (m) Wang, L-C.; Luis, A. L.; Agapiou, K.; Jang, H.-Y.; Krische, M. J. J. Am. Chem. Soc. 2002, 124, 2402.
21. (n) Frank, S. A.; Mergott, D. J.; Roush, W. R. J. Am. Chem. Soc. 2002, 124, 2404.
22. (a) Augé, J.; Lubin, N.; Lubineau, A. Tetrahedron Lett. 1994, 35, 7947.
23. (b) Yu, C.; Liu, B.; Hu, L. J. Org. Chem. 2001, 66, 5413.
24. (c) Cai, J.; Zhou, Z.; Zhao, G.; Tang, C. Org. Lett. 2002, 4, 4723.
25. For a systematic examination of the influence of protic and high-dielectric solvents on the Baylis-Hillman reaction, see: Aggarwal, V. K.; Dean, D. K.; Mereu, A.; Williams, A. J. Org. Chem. 2002, 67, 510.
26. Kawamura, M.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 1539.
27. (a) Li, G.; Wei, H. X.; Gao, J.; Caputo, T. D. Tetrahedron Lett. 2000, 41, 1.
28. (b) Basavaiah, D.; Sreenivasulu, B.; Reddy, R. M.; Muthukumaran, K. Synth. Commun. 2001, 31, 2987.
29. (c) Basavaiah, D.; Sreenivasulu, B.; Rao, A. J. J. Org. Chem. 2003, 68, 5983.
30. (d) Aggarwal, V. K.; Tarver, G. J.; McCague, R. Chem. Commun. 1996, 2713.
31. (e) Aggarwal, V. K.; Mereu, A.; Tarver, G. J.; McCague, R. J. Org. Chem. 1998, 63, 7183.
32. (f) Shi, M.; Jiang, J.-K.; Cui, S.-K. Molecules 2001, 6, 852.
33. Yu, C.; Hu, L. J. Org. Chem. 2002, 67, 219.
34. Krishna and co-workers have recently reported an isolated example of the reaction between p-nitro-benzaldehyde and acrylamide in sulfolane as solvent: Krishna, P. R.; Manjuvani, A.; Sharma, G. V. M. Tetrahedron Lett. 2004, 45, 1183.
35. Duffy, D. M.; Rodger, P. M. J. Am. Chem. Soc. 2002, 124, 5206.
36. (a) Ohmori, Y.; Yamashita, A.; Tsujita, R.; Yamamoto, T.; Taniuchi, K.; Matsuda, A.; Shuto, S. J. Med. Chem. 2003, 46, 5326.
37. (b) Song, Y.; Clizbe, L.; Bhakta, C.; Teng, W.; Wong, W.; Huang, B.; Tran, K.; Sinha, U.; Park, G.; Reed, A.; Scarborough, R. M.; Zhu, B.-Y. Bioorg. Med. Chem. Lett. 2003, 13, 297.
38. (c) Song, Y.; Clizbe, L.; Bhakta, C.; Teng, W.; Li, W.; Wu, Y.; Jon Jia, Z.; Zhang, P.; Wang, L.; Doughan, B.; Su, T.; Kanter, J.; Woolfrey, J.; Wong, P.; Huang, B.; Tran, K.; Sinha, U.; Park, G.; Reed, A.; Malinowski, J.; Hollenbach, S.; Scarborough, R. M.; Zhu, B.-Y. Bioorg. Med. Chem. Lett. 2002, 12, 1511.
39. (a) Hill, J. S.; Issacs, N. S. J. Phys. Org. Chem. 1990, 3, 285.
40. (b) Bode M. L.; Kaye, P. T. Tetrahedron Lett. 1991, 32, 5611.
41. For studies concerning the stability of amide tautomers, see: (a) Mukhopadhyaya, J. K.; Sklenák, S.; Rappoport, Z. J. Am. Chem. Soc. 2000, 122, 1325.
42. (b) Lei Y. X.; Casarini, D.; Cerioni, G.; Rappoport, Z. J. Org. Chem. 2003, 68, 947.
43. (c) Basheer, A.; Rappoport, Z. J. Org. Chem. 2004, 69, 1151.
44. For use of trialkylphosphines under high pressure, see: (a) Jenner, G. Tetrahedron Lett. 2001, 42, 4807.
45. (b) Jenner, G. Tetrahedron 2002, 58, 4311.
46. For use of trialkylphosphines under atmospheric pressure, see: (a) Kasinga, P. B.; Ilankumaran P.; Fetterly, B. M.; Verkade J. G. J. Org. Chem. 2002, 67, 3555.
47. (b) Stewart, I. C.; Bergman, R. G.; Toste, F. D. J. Am. Chem. Soc. 2003, 125, 8696.
48. a values (25 °C) are taken from (a) (quinuclidine and 3-hydroxyquinuclidine) Grob, C. A. Helv. Chim. Acta 1985, 68, 882.
49. (b) (DABCO) Hine, J.; Kaufmann, C.; Cholod, S. J. Am. Chem. Soc. 1987, 52, 2091.
50. (c) (DMAP) Chrystuik, E.; Williams, A. J. Am. Chem. Soc. 1987, 109, 3040.
51. (d) (TEA) Kuna S.; Pawlak, Z.; Tusk, M. J. Chem. Soc., Faraday Trans. 1982, 78, 2685.
52. 3P) Henderson, W. A.; Streuli, C. A. J. Am. Chem. Soc. 1960, 82, 5791.
53. (f) (DIPEA) Fujii, T.; Nishida, H.; Abiru, Y.; Yamamoto, M.; Kise, M. Chem. Pharm. Bull. 1995, 43, 1872.
54. 8) α to the carbonyl moiety in the presence of DABCO. The rate of exchange was found to be strongly dependent on the catalyst loading.
55. N2-type displacement of the ammonium moiety from A by alkoxide ion is an alternative mechanistic possibility. However, few examples of such reactions exist in the literature.
56. It is worth noting at this juncture that the possibility of both uncatalyzed addition of MeOH to acrylamide (Table 1, entry 1) and direct Brønsted-base catalysis by the amine nucleophiles (Table 1, entries 6 and 7) have been experimentally excluded.
57. 3) δ 3.14 (t, 2H, J = 6.5 Hz), 3.24 (s, 6H), 4.51 (t, 2H, J = 6.5 Hz), 6.81 (d, 2H, J = 7.5 Hz), 8.46 (d, 2H, J = 7.5 Hz). After 1.16 h reaction time ca. 2% of the DMAP catalyst had converted to A.
58. Using DABCO as a catalyst, intermediate A was not observed, indicating that its equilibrium concentration is considerably lower than that observed using DMAP.
59. Bergman, Toste et al. (ref 15b) unambiguously identified β-phosphonium ketones (analogous to A) as intermediates in hydroalkoxylation reactions of ketones catalyzed by trialkylphosphines.
60. For the use of phenols as an additive in phosphine-catalyzed Baylis-Hillman reactions, see: (a) Yamada, Y. M. A.; Ikegami, S. Tetrahedron Lett. 2000, 41, 2165.
61. (b) McDougal, N. T.; Schaus, S. E. J. Am. Chem. Soc. 2003, 125, 12094.
62. The phenoxide anion is not nucleophilic enough to undergo a hydroalkoxylation reaction with acrylamide, as no such addition products are observed.
63. The use of phenol in conjunction with other, more basic amines such as DMAP resulted in dramatically reduced reaction rates due to protonation and deactivation of the catalyst.
64. It was also possible to carry out this reaction on a multigram scale in reproducible yield.
65. It is noteworthy that these reactions are verifiably reversible: when isolated Baylis-Hillman adduct 4 is resubjected to the reaction conditions (diluted by a factor of 2) an equilibration occurs, giving a mixture containing ca. 7:3 ratio of 4:acrylamide after 5 days