Palladium-catalyzed benzene arylation: Incorporation of catalytic pivalic acid as a proton shuttle and a key element in catalyst design

Journal of the American Chemical Society

Volumn 128, Issue 51, 2006, Pages 16496-16497

  Lafrance, Marc ^a   Fagnou, Keith ^a  

^a UNIVERSITY OF OTTAWA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE; PALLADIUM; PIVALIC ACID;

ARTICLE; ARYLATION; CATALYSIS; CATALYST; DENSITY FUNCTIONAL THEORY; HYDROGEN BOND; PROTON TRANSPORT; QUANTUM YIELD; REACTION ANALYSIS; STEREOSPECIFICITY;

ALKYLATION; BENZENE; CATALYSIS; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; PALLADIUM; PENTANOIC ACIDS; PROTONS; STEREOISOMERISM;

EID: 33845938814     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja067144j     Document Type: Article

References (36)

1. Hassa, J.; Sevignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M. Chem. Rev. 2002, 102, 1359.
2. For recent reviews, see the following: (a) Kakiuchi, F.; Murai, S. Acc. Chem. Res. 2002, 35, 826.
3. (b) Ritleng, V.; Sirlin, C.; Pfeffer, M. Chem. Rev. 2002, 102, 1731.
4. (c) Miura, M.; Nomura, M. Top. Curr. Chem. 2002, 219, 211.
5. (d) Kakiuchi, F.; Chatani, N. Adv. Synth. Catal. 2003, 345, 1077.
6. (e) Campeau, L.-C.; Fagnou, K. Chem. Commun. 2005, 1253.
7. Akita, Y.; Itagaki, Y.; Takizawa, S.; Ohta, A. Chem. Pharm. Bull 1989, 37, 1477.
8. For recent examples involving metallacyclic intermediates, see: (a) Daugulis, O.; Zaitsev, V. G. Angew. Chem., Int. Ed. 2005, 44, 4046.
9. (b) Kalyani, D.; Deprez, N. R.; Desai, L. V.; Sanford, M. S. J. Am. Chem. Soc. 2005, 127, 7330.
10. (c) Kakiuchi, F.; Kan, S.; Igi, K.; Chatani, N.; Murai, S. J. Am. Chem. Soc. 2003, 125, 1698.
11. (d) Bedford, R. B.; Coles, S. J.; Hursthouse, M. B.; Limmert, M. E. Angew. Chem., Int. Ed. 2003, 42, 112.
12. For recent advances with electron-rich heterocycles, see: (a) Lane, B. S.; Brown, M. A.; Sames, D. J. Am. Chem. Soc. 2005, 127, 8050.
13. (b) Park, C. H.; Ryabova, V.; Seregin, I. V.; Sromek, A. W.; Gevorgyan, V. Org. Lett. 2004, 6, 1159.
14. (c) Li, W. J.; Nelson, D. P.; Jensen, M. S.; Hoerrner, R. S.; Javadi, G. J.; Cai, D.; Larsen, R. D. Org. Lett. 2003, 5, 4835.
15. (d) Mori, A.; Sekiguchi, A.; Masui, K.; Shimada, T.; Horie, M.; Osakada, K.; Kawamoto, M.; Ikeda, T. J. Am. Chem. Soc. 2003, 125, 1700.
16. (e) Yanagisawa, S.; Sudo, T.; Noyori, R.; Itami, K. J. Am. Chem. Soc. 2006, 128, 11749.
17. For recent examples of intramolecular reactions with simple arenes, see: (a) Campeau, L.-C.; Parisien, M.; Jean, A.; Fagnou, K.; J. Am. Chem. Soc. 2006, 128, 581.
18. (b) Huang, Q.; Fazio, A.; Dai, G.; Campo, M. A.; Larock, R. C. J. Am. Chem. Soc. 2004, 126, 7460.
19. (c) Garcia-Cuadrado, D.; Braga, A. A. C.; Maseras, F.; Echavarren, A. M. J. Am. Chem. Soc. 2006, 128, 1066.
20. Lafrance, M.; Rowley, C. N.; Woo, T. K.; Fagnou, K. K. J. Am. Chem. Soc. 2006, 128, 8754.
21. We have previously observed a poisoning effect on direct arylation by the presence of iodide salts (see ref 6a).
22. In polar media, an excess of anionic ligands could result in the formation of palladate species which may prevent the arene from binding and achieving C-H bond cleavage. For a discussion of palladates in cross-coupling reactions, see: Amatore, C.; Jutand, A. Acc. Chem. Res. 2000, 33, 314.
23. We differentiate these reactions from arylations with aryl radicals whose generation is catalyzed by metals, see: (a) Mukhopadhyay, S.; Rothenberg, G.; Gitis, D.; Baidossi, M.; Ponde, D. E.; Sasson, Y. J. Chem. Soc., Perkin Trans. 2 2000, 1809.
24. (b) Fujita, K.-i.; Nonogawa, M.; Yamaguchi, R. Chem. Commun. 2004, 1926.
25. Harris, M. C.; Geis, O.; Buckwald, S. L. J. Org. Chem. 1999, 64, 6019.
26. The choice of ligand is less crucial than the choice of base and additive. This will be discussed further in a full account of this work.
27. Bancroft, D. P.; Cotton, F. A.; Falvello, L. R.; Schwotzer, W. Polyhedron 1988, 7, 615.
28. Larock has employed CsOPiv as a stoichiometric base for migratory processes (ref 6b). Here, the use of Cs salts results in inferior outcomes as we have observed elsewhere (ref 6a).
29. These byproducts account for the remainder of the converted mass balance in approximately equal measure. The percent conversion is based on the amount of aryl bromide consumed during the reaction.
30. 3 had dissolved.
31. See Supporting Information for experimental details.
32. For pertinent mechanistic studies, see: (a) Kobayashi, M.; Minato, H.; Kobori, N. Bull. Chem. Soc. Jpn. 1969, 42, 2738.
33. (b) Eliel, E. L.; Welvart, Z.; Wilen, S. H. J. Org. Chem. 1958, 23, 1821.
34. (c) Davies, D. I.; Hey, D. H.; Summers, B. J. Chem. Soc. C 1971, 2682.
35. (d) Beadle, J. R.; Korzeniowski, S. H.; Rosenburg, D. E.; Garcia-Slanga, B. J.; Gokel, G. W. J. Org. Chem. 1984, 49, 1591.
36. B3LYP density-functional theory calculations were performed with the Jaguar 6.0 package with the LACV3P+** basis set and pseudopotential combination of Jaguar. Full details are provided in the Supporting Information.