A general method for the direct α-arylation of aldehydes with aryl bromides and chlorides

Angewandte Chemie - International Edition

Volumn 46, Issue 38, 2007, Pages 7236-7239

  Martín, Rubén ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Aldehydes; Arylation; Homogeneous catalysis; P ligands; Palladium

Indexed keywords

ALDEHYDES; CATALYST ACTIVITY; LIGANDS; PALLADIUM; SYNTHESIS (CHEMICAL);

ARYLATION; FUNCTIONALIZED COMPOUNDS; SUBSTITUTION PATTERNS;

REACTION KINETICS;

ALDEHYDE; BROMIDE; CHLORIDE; PALLADIUM;

ARTICLE; CATALYSIS; CHEMISTRY;

ALDEHYDES; BROMIDES; CATALYSIS; CHLORIDES; PALLADIUM;

EID: 34948878232     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200703009     Document Type: Article

References (34)

1. a) S. Yokoshima, T. Uedo, S. Kobayashi, A. Sato, T. Kuboyama, H. Tokuyama, T. Fukuyama, J. Am. Chem. Soc. 2002, 124, 2137-2139;
2. b) H. Venkatesan, M. C. Davis, Y. Altas, J. P. Snyder, D. C. Liotta, J. Org. Chem. 2001, 66, 3653-3661;
3. c) S. Edmondson, S. J. Danishefsky, L. Sepp-Lorenzino, N. Rosen, J. Am. Chem. Soc. 1999, 121, 2147;
4. d) T. Y. Shen, Angew. Chem. 1972, 84, 512-526;
5. Angew. Chem. Int. Ed. Engl. 1972, 11, 460-472.
6. Selected references on α-arylation of ketones: a) J. M. Fox, X. Huang, A. Chieffi, S. L. Buchwald. J. Am. Chem. Soc. 2000, 122, 1360-1370;
7. b) M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 1999, 121, 1473-1478.
8. Selected references on α-arylation of esters: a) T. Hama, X. Liu, D. A. Culkin, J. F. Hartwig, J. Am. Chem. Soc. 2003, 125, 11176-11177;
9. b) W. A. Moradi, S. L. Buchwald, J. Am. Chem. Soc. 2001, 123, 7996-8002.
10. Selected references on α-arylation of amides: a) T. Hama, D. A. Culkin, J. F. Hartwig, J. Am. Chem. Soc. 2006, 128, 4976-4985;
11. b) S. Lee, J. F. Hartwig, J. Org. Chem. 2001, 66, 3402-3415.
12. Enantioselective protocols: a) D. J. Spielvogel, S. L. Buchwald, J. Am. Chem. Soc. 2002, 124, 3500-3501;
13. b) T. Hamada, A. Chieffi, J. Åhman, S. L. Buchwald, J. Am. Chem. Soc. 2002, 124, 1261-1268;
14. c) J. Åhman, J. P. Wolfe, M. V. Troutman, M. Palucki, S. L. Buchwald, J. Am. Chem. Soc. 1998, 120, 1918-1919.
15. Very recently, an organocatalytic α-arylation of aldehydes using quinones as a coupling partner has been reported: J. Alemán, S. Cabrera, E. Maerten, J. Overgaard, K. A. Jørgensen, Angew. Chem. 2007, 119, 5616-5619;
16. Angew. Chem. Int. Ed. 2007, 46, 5520-5523.
17. Y. Terao, Y. Fukuoka, T. Satoh, M. Miura, M. Nomura, Tetrahedron Lett. 2002, 43, 101-104.
18. For an intramolecular α-arylation of formyl groups, see: H. Muratake, M. Natsume, H. Nakai, Tetrahedron 2004, 60, 11783-11803.
19. D. A. Culkin, J. F. Hartwig, Acc. Chem. Res. 2003, 36, 234-245.
20. Retroaldol adducts from ketones have been used as aldehyde surrogates: a) B. Xi, V. Nevalainen, Tetrahedron Lett. 2006, 47, 2561-2564;
21. b) I. Simpura, V. Nevalainen, Angew. Chem. 2000, 112, 3564-3567;
22. Angew. Chem. Int. Ed. 2000, 39, 3422-3425.
23. For experimental details, see the Supporting Information.
24. Presumably the water inhibits dehydration of the aldol product.
25. T. Hamada, A. Chieffi, J. Ahman, S. L. Buchwald, J. Am. Chem. Soc. 2002, 124, 1261-1268.
26. Y. Terao, T. Satoh, M. Miura, M. Nomura, Tetrahedron Lett. 1998, 39, 6203-6206.
27. A related cyclization in moderate yield using ortho-iodoanilines has been recently reported, although no mechanism was proposed: C. S. Cho, H. S. Shim, H.-J. Choi, T.-J. Kim, S. C. Shim, Bull. Korean Chem. Soc. 2004, 25, 441-444.
28. For a recent review on the synthesis of the indole core, see: G. R. Humphrey, J. T. Kuethe, Chem. Rev. 2006, 106, 2875-2911.
29. C-Y. Chen, R. D. Larsen, Org. Synth. 2002, 78, 36-39.
30. This explanation is supported by the fact that neither 3- nor 4-bromoaniline provided α-arylated or γ-arylated compounds by reaction with hexanal.
31. At present, the available mechanistic information does not allow us to rule alternative pathways out. Thus, an intramolecular Heck reaction from the enamine intermediate could also be considered: J. Barluenga, M. A. Fernández, F. Aznar, C. Valdés, Chem. Eur. J. 2005, 11, 2276-2283.
32. For a review, see: J. Christoffers, A. Baro, Adv. Synth. Catal. 2005, 347, 1473-1482.
33. T. E. Barder, S. D. Walker, J. R. Martinelli, S. L. Buchwald, J. Am. Chem. Soc. 2005, 127, 4685-4696.
34. A. B. Northrup, D. W. C. MacMillan, J. Am. Chem. Soc. 2002, 124, 6798-6799.