AuX3-mediated selective head-to-head dimerization of difluoropropargyl amides

Journal of Organic Chemistry

Volumn 74, Issue 20, 2009, Pages 7690-7696

  Fustero, Santos ^a,b   Bello, Paula ^a   Fernández, Begoña ^a   Del Pozo, Carlos ^a   Hammond, Gerald B ^c  

^a UNIVERSITY OF VALENCIA   (Spain)

^b CENTRO DE INVESTIGACIÓN PRÍNCIPE FELIPE   (Spain)

^c UNIVERSITY OF LOUISVILLE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL EQUATIONS; REDUCTIVE ELIMINATION;

CHEMICAL REACTIONS; DIMERIZATION; GOLD COMPOUNDS; OLEFINS;

AMIDES;

AMIDE; GOLD; HALIDE;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; CRYSTAL STRUCTURE; DIMERIZATION; FLUORINATION; MICROWAVE IRRADIATION; SYNTHESIS;

EID: 70349861773     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9013436     Document Type: Article

References (46)

1. (a) Hutchings, G. J.; Brust, M.; Schmidbaur, H. Chem. Soc. Rev. 2008, 37, 1759.
2. (b) Li, Z.; Brouwer, C.; He, C. Chem. Rev. 2008, 108, 3239.
3. (c) Hashmi, A. S. K. Chem. Rev. 2007, 107, 3180.
4. For selected recent reviews, see: (a) Nuñez, E. J.; Echavarren, A. Chem. Rev. 2008, 108, 3326.
5. (b) Gorin, D. J.; Sherry, B. D.; Toste, F. D. Chem. Rev. 2008, 108, 3351.
6. (c) Muzart, J. Tetrahedron 2008, 64, 5815.
7. (d) Shen, H. C. Tetrahedron 2008, 64, 7847.
8. For selected recent reviews, see: (a) Arcadi, A. Chem. Rev. 2008, 108, 3266.
9. (b) Skouta, R.; Li, C.-J. Tetrahedron 2008, 64, 4917.
10. (a) Soloshonok, V. A.; Kacharov, A. D.; Hayashi, T. Tetrahedron 1996, 52, 245.
11. (b) Soloshonok, V. A.; Hayashi, T. Tetrahedron Lett. 1994, 35, 1091.
12. (c) Soloshonok, V. A.; Hayashi, T. Tetrahedron Lett. 1994, 35, 2713.
13. (a) Soloshonok, V. A.; Kacharov, A. D.; Avilov, D. V.; Ishikawa, K.; Nagashima, M.; Hayashi, T. J. Org. Chem. 1997, 62, 3470.
14. (b) Soloshonok, V. A.; Kacharov, A. D.; Avilov, D. V.; Hayashi, T. Tetrahedron Lett. 1996, 37, 7845.
15. (c) Soloshonok, V. A.; Hayashi, T.; Ishikawa, K.; Nagashima, N. Tetrahedron Lett. 1994, 35, 1055.
16. Hayashi, T.; Kishi, E.; Soloshonok, V. A.; Uozumi, Y. Tetrahedron Lett. 1996, 37, 4969.
17. Akana, J. A.; Bhattacharyya, K. X.; Muller, P.; Sadighi, J. P. J. Am. Chem. Soc. 2007, 129, 7736.
18. Schuler, M.; Silva, F.; Bobbio, C.; Tessier, A.; Gouverneur, V. Angew. Chem., Int. Ed. 2008, 47, 7927.
19. Surmont, R.; Verniest, G.; De Kimpe, N. Org. Lett. 2009, 11, 2920 and references cited therein.
20. (a) Fustero, S.; Fernández, B.; Bello, P.; del Pozo, C.; Arimitsu, S.; Hammond, G. B. Org. Lett. 2007, 9, 4251.
21. (b) Arimirtsu, S.; Fernández, B.; del Pozo, C.; Fustero, S.; Hammond, G. B. J. Org. Chem. 2008, 73, 2656.
22. For the X-ray structure of 2a, see the Supporting Information.
23. 3 has been recently reported, although as a side reaction product. A reductive elimination of gold(III) species was invoked to explain its formation: Hashmi, A. S. K.; Blanco, M. C.; Fischer, D.; Bats, J. W. Eur. J. Org. Chem. 2006, 1387.
24. 2 no formation of dimeric derivatives was detected.
25. When internal alkynes in the starting amides 1 were used, the recovery of the starting material was observed in all cases studied.
26. We had previously observed this behavior in the intramolecular hydroamination reaction of fluorinated amide 1a mediated by TBAF. See ref 10a.
27. Gold is not usually involved in redox catalytic cycles: Gorin, D. G.; Toste, D. N. Nature 2007, 446, 395.
28. 2. Its formation was assumed considering that when no other nucleophile is present, the corresponding gold-alkyne π complex reacts with a chloride ion: Reetz, M. T.; Sommer, K. Eur. J. Org. Chem. 2003, 3485.
29. The use of gold complexes in stoichiometric reactions is rare. For a recent example, see: (a) Sahoo, A. K.; Nakamura, Y.; Aratani, N.; Kim, K. S.; Noh, S. B.; Shinokubo, H.; Kim, D.; Osuka, A. Org. Lett. 2006, 8, 4141.
30. See also: (b) Fuchita, Y.; Utsinomiya, Y.; Yasutake, M. J. Chem. Soc., Dalton Trans. 1 2001, 2330.
31. (c) Zamora, F.; Amo-Ochoa, P.; Fischer, B.; Schimanski, A.; Lippert, B. Angew. Chem., Int. Ed. 1999, 38, 2274.
32. Kar, A.; Mangu, N.; Kaiser, H. M.; Beller, M.; Tse, M. K. Chem. Commun. 2008, 386.
33. Wegner, H. A.; Ahles, S.; Neuburger, M. Chem. - Eur. J. 2008, 14, 11310.
34. LiCl was very recently used as halogen source in chloropalladation reactions of a triple bond: Yin, G.; Liu, G. Angew. Chem., Int. Ed. 2008, 47, 5442.
35. 2 was used both as oxidant additive and halogen source in palladium-catalyzed reactions: (a) Tang, S.; Yu, Q.-F.; Peng, P.; Li, J.-H.; Zhong, P.; Tang, R.-Y. Org. Lett. 2007, 9, 3413.
36. (b) Ma, S.; Wu, B.; Zhao, S. Org. Lett. 2003, 5, 4429.
37. 1,4-Benzoquinone was used for the reoxidation of Pd(0) to Pd(II): (a) Piera, J.; Persson, A.; Caldentey, X.; Bäckvall, J.-E. J. Am. Chem. Soc. 2007, 129, 14120.
38. (b) Piera, J.; Närhi, K.; Bäckvall, J.-E. Angew. Chem., Int. Ed. 2006, 45, 6914.
39. 5 was used as additive, only the product derived from the hydroamination of the amidic-nitrogen over the triple bond was observed.
40. Probably the driving force of this process would be the generation of more conjugation along the backbone of product 4.
41. For the preparation of compound 6, see the Supporting Information.
42. For a recent review of the preparation of multiply substituted butadiene containing building blocks, see: Xi, Z.; Zhang, W.-X. Synlett 2008, 2557.
43. Zhao, Q.; Li, C. Org. Lett. 2008, 10, 4037 and references cited therein.
44. For recent examples, see: (a) Jiang, B.; Tian, H.; Huang, Z.-G.; Xu, M. Org. Lett. 2008, 10, 2737.
45. (b) Toumi, M.; Couty, F.; Evano, G. Angew. Chem., Int. Ed. 2007, 46, 572.
46. The configuration of the double bond in compound 12 was not determined.