A meta-selective copper-catalyzed C-H bond arylation

Science

Volumn 323, Issue 5921, 2009, Pages 1593-1597

  Phipps, Robert J ^a   Gaunt, Matthew J ^a  

^a UNIVERSITY OF CAMBRIDGE   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; COPPER; HYDROGEN;

BENZENE; CATALYSIS; CHEMICAL BONDING; COPPER; ELECTRON; HYDROGEN; TRANSFORMATION;

ARTICLE; ARYLATION; CATALYSIS; CHEMICAL BOND; ELECTRON; ENZYME SUBSTRATE; HYDROGEN BOND; PRIORITY JOURNAL;

ACETANILIDES; ANILIDES; BENZENE; CARBON; CATALYSIS; CHEMICAL PHENOMENA; COPPER; HYDROGEN; ISOMERISM; MOLECULAR STRUCTURE; OXIDATION-REDUCTION;

EID: 62849102089     PISSN: 00368075     EISSN: 10959203     Source Type: Journal    
DOI: 10.1126/science.1169975     Document Type: Article

References (43)

1. J. Hassan, M. Sevignon, C. Gozzi, E. Schulz, M. Lemaire, Chem. Rev. 102, 1359 (2002).
2. G. A. Olah, Friedel-Crafts and Related Reactions (Wiley, New York, 1963).
3. C. Friedel, J. M. Crafts, Comptes Rendus 84, 1392 (1877).
4. C. J. Rohbogner, G. C. Clososki, P. Knochel, Angew. Chem. Int. Ed. 47, 1503 (2008).
5. J. P. Flemming, M. B. Berry, J. M. Brown, Org. Biomol. Chem. 6, 1215 (2008).
6. R. E. Mulvey, F. Mongin, M. Uchiyama, Y. Kondo, Angew. Chem. Int. Ed. 46, 3802 (2007).
7. V. Snieckus, Chem. Rev. 90, 879 (1990).
8. D. Alberico, M. E. Scott, M. Lautens, Chem. Rev. 107, 174 (2007).
9. K. Godula, D. Sames, Science 312, 67 (2006).
10. R. J. Phipps, N. P. Grimster, M. J. Gaunt, J. Am. Chem. Soc. 130, 8172 (2008) and references therein.
11. N. P. Grimster, C. Gauntlett, C. R. A. Godfrey, M. J. Gaunt, Angew. Chem. Int. Ed. 44, 3125 (2005).
12. E. M. Beck, N. P. Grimster, R. Hatley, M. J. Gaunt, J. Am. Chem. Soc. 128, 2528 (2006).
13. D. R. Stuart, K. Fagnou, Science 316, 1172 (2007).
14. D. R. Stuart, E. Villemure, K. Fagnou, J. Am. Chem. Soc. 129, 12072 (2007).
15. L.-C. Campeau, D. J. Schipper, K. Fagnou, J. Am. Chem. Soc. 130, 3266 (2008).
16. C. Jia, T. Kitamura, Y. Fujiwara, Acc. Chem. Res. 34, 633 (2001) and references therein.
17. M. Lafrance, K. Fagnou, J. Am. Chem. Soc. 128, 16496 (2006).
18. D. Garcia-Cuadrado, A. A. C. Braga, F. Maseras, A. M. Echavarren, J. Am. Chem. Soc. 128, 1066 (2006).
19. D. L. Davies, S. M. A. Donald, S. A. Macgregor, J. Am. Chem. Soc. 127, 13754 (2005).
20. For an overview of C-H bond functionalization on acetanilides, see (21, 36).
21. G. Brasche, J. Garcia-Fortanet, S. L. Buchwald, Org. Lett. 10, 2207 (2008).
22. For an example of pyridine directed ortho-C-H arylation, see (37).
23. For Cu(II)-catalyzed, pyridine-directed, C-H bond functionalization, see (38).
24. For a recent example of carboxylate directed ortho-C-H bond arylation, see (39).
25. For imine-directed C-H bond functionalization, see (40).
26. For ketone-directed C-H bond functionalization, see (41).
27. J.-Y. Cho, M. K. Tse, D. Holmes, R. E. Maleczka Jr., M. R. Smith III, Science 295, 305 (2002).
28. J. M. Murphy, X. Liao, J. F. Hartwig, J. Am. Chem. Soc. 129, 15434 (2007) and references therein.
29. D. H. R. Barton, J. P. Finet, J. Khamsi, Tetrahedron Lett. 28, 887 (1987).
30. N. R. Deprez, D. Kalyani, A. Krause, M. S. Sanford, J. Am. Chem. Soc. 128, 4972 (2006).
31. Materials and methods are available as supporting material on Science Online.
32. O. Daugulis, V. G. Zaitsev, Angew. Chem. Int. Ed. 44, 4046 (2005).
33. We cannot rule out coordination of the Cu(III) species at the ortho position, followed by a migration to the meta site and arylation. However, we do not see any sign of ortho-arylation that may be expected through this pathway. For example, see (42).
34. The pivaloyl amide moiety in 2f can be cleaved to the corresponding amine (95% yield) on treatment with HCl-EtOH at 100°C (see supporting online material).
35. M. Bielawski, M. Zhu, B. Olofsson, Adv. Synth. Catal. 349, 2610 (2007).
36. B.-J. Li, S.-D. Yang, Z.-J. Shi, Synlett 2008, 949 (2008) and references therein.
37. L. V. Desai, K. J. Stowers, M. S. Sanford, J. Am. Chem. Soc. 130, 13285 (2008).
38. X. Chen, X.-S. Hao, C. E. Goodhue, J.-Q. Yu, J. Am. Chem. Soc. 128, 6790 (2006).
39. D.-H. Wang, T.-S. Mei, J.-Q. Yu, J. Am. Chem. Soc. 130, 14082 (2008).
40. R. K. Thalji, J. A. Ellman, R. G. Bergman, J. Am. Chem. Soc. 126, 7172 (2004).
41. S. Murai et al., Nature 366, 529 (1993).
42. G. Evindar, R. A. Batey, J. Org. Chem. 71, 1802 (2006).
43. We gratefully acknowledge the Biotechnology and Biological Sciences Research Council and GlaxoSmithKline for an Industrial Case Award to R.J.P., the Royal Society for a University Research Fellowship to M.J.G., and Philip and Patricia Brown for a Next Generation Fellowship to M.J.G. We also thank S. Peace (GSK Medicines Research Center, UK) for useful discussion.