The first conjugate addition reaction of terminal alkynes catalytic in copper: Conjugate addition of alkynes in water

Journal of the American Chemical Society

Volumn 125, Issue 20, 2003, Pages 6054-6055

  Knöpfel, Thomas F ^a   Carreira, Erick M ^a  

^a ETH ZURICH   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; COPPER DERIVATIVE; WATER;

AQUEOUS SOLUTION; ARTICLE; CATALYSIS; CHEMICAL BOND; ELECTRON TRANSPORT; REACTION ANALYSIS; STOICHIOMETRY; WATER CONTENT;

EID: 0037613482     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja035311z     Document Type: Article

References (46)

1. Kanai, M.; Shibasaki, M. In Catalytic Asymmetric Synthesis, 2nd ed.; Ojima, I., Ed.; Wiley-VCH: New York, 2000; pp 569-592.
2. Corey, E. J.; Naef, R.; Hannon, F. J. J. Am. Chem. Soc. 1986, 108, 7114-7116.
3. Krause. N. Modern Organocopper Chemistry; Wiley-VCH: Weinheim, 2002.
4. Feringa, B. L. Acc. Chem. Res. 2000, 33, 346-353.
5. Alexakis, A.; Benhaim, C.; Rosse, S.; Humam, M. J. Am. Chem. Soc. 2002, 124, 5262-5263.
6. Pichota, A.; Pregosin, P. S.; Valentini, M.; Worle, M.; Seebach, D. Angew. Chem., Int. Ed. 2000, 39, 153-156.
7. Xie, X. L.; Auel, C.; Henze, W.; Gschwind, R. M. J. Am. Chem. Soc. 2003, 125, 1595-1601.
8. Hird, A. W.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2003, 42, 1276-1279.
9. Corey, E. J.; Beames, D. J. J. Am. Chem. Soc. 1972, 94, 7210-7211.
10. Hooz, J.; Layton, R. B. J. Am. Chem. Soc. 1971, 93, 7320-7322.
11. Pappo, R.; Collins, P. W. Tetrahedron Lett. 1972, 13, 2627-2630.
12. Bruhn, M.; Brown, C. H.; Collins, P. W.; Palmer, J. R.; Dajani, E. Z.; Pappo, R. Tetrahedron Lett. 1976, 17, 235-238.
13. Schwartz, J.; Carr, D. B.; Hansen, R. T.; Dayrit, F. M. J. Org. Chem. 1980, 45, 3053-3061.
14. Sinclair, J. A.; Molander, G. A.; Brown, H. C. J. Am. Chem. Soc. 1977, 99, 954-956.
15. Kim, S.; Lee, J. M. Tetrahedron Lett. 1990, 31, 7627-7630.
16. Bergdahl, M.; Eriksson, M.; Nilsson, M.; Olsson, T. J. Org. Chem. 1993, 58, 7238-7244.
17. Eriksson, M.; Iliefski, T.; Nilsson, M.; Olsson, T. J. Org. Chem. 1997, 62, 182-187.
18. Kim S.; Park, J. H.; Jon, S. Y. Bull. Korean Chem. Soc. 1995, 16, 783-786.
19. Conjugate addition reactions of terminal acetylenes using late transition-metal catalysts (Rh, Ru) have been documented. However, these reactions are limited to unsubstituted vinyl ketones, see: Kovalev, I. P.; Nikishin, G. I. Tetrahedron Lett. 1990, 31, 7063-7064. (b) Chang, S.; Na, Y.; Choi, E.; Kim, S. Org. Lett. 2001, 3, 2089-2091.
20. Conjugate addition reactions of terminal acetylenes using late transition-metal catalysts (Rh, Ru) have been documented. However, these reactions are limited to unsubstituted vinyl ketones, see: Kovalev, I. P.; Nikishin, G. I. Tetrahedron Lett. 1990, 31, 7063-7064. (b) Chang, S.; Na, Y.; Choi, E.; Kim, S. Org. Lett. 2001, 3, 2089-2091.
21. Pd-catalyzed addition of terminal acetylenes to acceptor alkynes has been reported by Trost. see: Trost, B. M.; Sorum, M. T.; Chan, C.; Harms, A. E.; Rühter, G. J. Am. Chem. Soc. 1997, 119, 698-708.
22. Trost, B. M.; Frontier, H. A. J. Am. Chem. Soc. 2000, 122, 11727-11728.
23. Frantz, D. E.; Fässler, R.; Carreira, E. M. J. Am. Chem. Soc. 2000, 122, 1806-1807.
24. Frantz, D. E.; Fässler, R.; Tomooka, C. S.; Carreira, E. M. Acc. Chem. Res. 2000, 33, 373-381.
25. Boyall, D.; Lopez, F.; Sasaki, H.; Frantz, D.; Carreira, E. M. Org. Lett. 2000, 2, 4233-4236.
26. Anand, N. K.; Carreira, E. M. J. Am. Chem. Cheiii. Soc. 2001, 123, 9687-9688.
27. El-Sayed, E.; Anand, N. K.; Carreira, E. M. Org. Lett. 2001, 3, 3017-3020.
28. Sasaki, H.; Boyall, D.; Carreira, E. M. Helv. Chim. Acta 2001, 84, 964-971.
29. Boyall, D.; Frantz, D. E.; Carreira, E. M. Org. Lett. 2002, 4, 2605-2606.
30. Reber, S.; Knöpfel, T. F.; Carreira, E. M. Tetrahedron 2003, submitted for publication.
31. Frantz, D. E.; Fässler, R.; Carreira, E. M. J. Am. Chem. Soc. 1999, 121, 11245-11246.
32. Aschwanden, P.; Frantz, D. E.; Carreira, E. M. Org. Lett. 2000, 2, 2331-2333.
33. Fässler, R.; Frantz, D. E.; Oetiker, J.; Carreira, E. M. Angew. Chem., Int. Ed. 2002, 41, 3054-3056.
34. Fischer, C.; Carreira, E. M. Org. Lett. 2001, 3, 4319-4321.
35. For reviews of Meldrum's acid. see: Chen, B. C. Heterocycles 1991, 32, 529-597.
36. Bigi, F.; Carloni, S.; Ferrari, L.; Maggi, R.; Mazzacani, A.; Sartori, G. Tetrahedron Lett. 2001, 42, 5203-5205.
37. For the use of alkylidene malonate derivatives, see: Evans, D. A.; Rovis, T.; Kozlowski, M. C.; Tedrow, J. S. J. Am. Chem. Soc. 1999, 121, 1994-1995.
38. Haslego, M. L.; Smith, F. X. Synth. Commun. 1980, 10, 421-427.
39. Huang, X.; Chan, C. C.; Wu, Q. L. Tetrahedron Lett. 1982, 23, 75-76.
40. Larcheveque, M.; Tamagnan, G.; Petit, Y. J. Chem. Soc., Chem. Commun. 1989, 31-33.
41. Glaser, C. Ber. 1869, 2, 422.
42. Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem., Int. Ed. 2002, 41, 2596-2599.
43. Davies, M. B. Polyhedron 1992, 11, 285-321.
44. At the current level of development, aliphatic substituted alkynes afford 5-10% yield adduct with 1b, and enynes such as 2-methyl-1-buten-3-yne furnish 20% yield of the corresponding adduct.
45. In our current working model, we believe that a Cu-acetylide is the key reactive intermediate. Preliminary observations involving the effect on the reaction of adding known ligands for copper are consistent with such a species.
46. Prices quoted are those for bulk quantities of material.