A highly para-selective copper(II)-catalyzed direct arylation of aniline and phenol derivatives

Angewandte Chemie - International Edition

Volumn 50, Issue 2, 2011, Pages 458-462

  Ciana, Claire Lise ^a   Phipps, Robert J ^a   Brandt, Jochen R ^a   Meyer, Falco Magnus ^a   Gaunt, Matthew J ^a  

^a UNIVERSITY OF CAMBRIDGE   (United Kingdom)

Author keywords

aromatic substitution; C H arylation; copper; hypervalent iodine; synthetic methods

Indexed keywords

AROMATIC GROUP; AROMATIC SUBSTITUTIONS; ARYLATIONS; COPPER (II); FRIEDEL-CRAFTS; FUNCTIONALIZATIONS; HYPERVALENT IODINE; META POSITIONS; PHENOL DERIVATIVES; SYNTHETIC METHODS;

ANILINE; AROMATIZATION; CATALYSIS; INDUSTRIAL CHEMICALS; IODINE; PHENOLS; POTASSIUM COMPOUNDS;

COPPER;

ANILINE; ANILINE DERIVATIVE; COPPER; IODINE; PHENOL;

ARTICLE; CATALYSIS; CHEMISTRY;

ANILINE COMPOUNDS; CATALYSIS; COPPER; IODINE; PHENOL;

EID: 78650891905     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201004703     Document Type: Article

References (61)

1. J. Hassan, M. Sevignon, C. Gozzi, E. Schulz, M. Lemaire, Chem. Rev. 2002, 102, 1359.
2. A. Podgorsek, M. Zupan, J. Iskra, Angew. Chem. 2009, 121, 8576
3. Angew. Chem. Int. Ed. 2009, 48, 8424.
4. For recent reviews on metal-catalyzed C-H bond functionalization, see
5. D. Alberico, M. E. Scott, M. Lautens, Chem. Rev. 2007, 107, 174
6. G. P. McGlacken, L. M. Bateman, Chem. Soc. Rev. 2009, 38, 2447
7. T. W. Lyons, M. S. Sanford, Chem. Rev. 2010, 110, 1147
8. X. Chen, K. M. Engle, D.-H. Wang, J.-Q. Yu, Angew. Chem. 2009, 121, 5196
9. Angew. Chem. Int. Ed. 2009, 48, 5094
10. M. Albrecht, Chem. Rev. 2010, 110, 576
11. D. A. Colby, R. G. Bergman, J. A. Ellman, Chem. Rev. 2010, 110, 624
12. L. Ackermann, R. Vicente, A. R. Kapdi, Angew. Chem. 2009, 121, 9976
13. Angew. Chem. Int. Ed. 2009, 48, 9792
14. F. Bellina, R. Rossi, Tetrahedron 2009, 65, 10269.
15. For direct arylations of electron-rich benzenes, see
16. M. Lafrance, K. Fagnou, J. Am. Chem. Soc. 2006, 128, 16496
17. B. Join, T. Yamamoto, K. Itami, Angew. Chem. 2009, 121, 3698
18. Angew. Chem. Int. Ed. 2009, 48, 3644
19. K.-I. Fujita, M. Nonogawa, R. Yamaguchi, Chem. Commun. 2004, 1926
20. W. Liu, H. Cao, A. Lei, Angew. Chem. 2010, 122, 2048
21. Angew. Chem. Int. Ed. 2010, 49, 2004
22. A. Voutchkova, A. Coplin, N. E. Leadbeater, R. H. Crabtree, Chem. Commun. 2008, 6312
23. T. Ishiyama, N. Miyaura, Pure Appl. Chem. 2006, 78, 1369. For a related C-H alkylation reaction, see
24. Y.-Z. Li, B.-J. Li, X.-Y. Lu, S. Lin, Z.-J. Shi, Angew. Chem. 2009, 121, 3875
25. Angew. Chem. Int. Ed. 2009, 48, 3817.
26. G. Brasche, J. Garcia-Fortanet, S. L. Buchwald, Org. Lett. 2008, 10, 2207.
27. Y. Kita, K. Morimoto, M. Ito, C. Ogawa, A. Goto, T. Dohi, J. Am. Chem. Soc. 2009, 131, 1668.
28. R. J. Phipps, N. P. Grimster, M. J. Gaunt, J. Am. Chem. Soc. 2008, 130, 8172
29. R. J. Phipps, M. J. Gaunt, Science 2009, 323, 1593.
30. M. Tobisu, T. Shimasaki, N. Chatani, Angew. Chem. 2008, 120, 4944
31. Angew. Chem. Int. Ed. 2008, 47, 4866.
32. E. A. Merritt, B. Olofsson, Angew. Chem. 2009, 121, 9214
33. Angew. Chem. Int. Ed. 2009, 48, 9052.
34. For a review of ortho-selective palladium(II)-catalyzed arylations of acetanilide, see
35. B.-J. Li, S.-D. Yang, Z.-J. Shi, Synlett 2008, 949; see also
36. O. Daugulis, V. G. Zaitsev, Angew. Chem. 2005, 117, 4114
37. Angew. Chem. Int. Ed. 2005, 44, 4046.
38. D. H. R. Barton, N. Y. Bhatnagar, J.-C. Blazejewski, B. Charpiot, J.-P. Finet, D. J. Lester, W. B. Motherwell, M. T. Barros Papoula, S. P. Stanforth, J. Chem. Soc. Perkin Trans. 1 1985, 2657
39. A. B. Edsall, A. K. Mohanakrishnan, D. Yang, P. E. Fanwick, E. Hamel, A. D. Hanson, G. E. Agoston, M. Cushman, J. Med. Chem. 2004, 47, 5126.
40. For examples of iterative C-H bond functionalization, see
41. E. M. Beck, R. Hatley, M. J. Gaunt, Angew. Chem. 2008, 120, 3046
42. Angew. Chem. Int. Ed. 2008, 47, 3004
43. E. M. Beck, N. P. Grimster, R. Hatley, M. J. Gaunt, J. Am. Chem. Soc. 2006, 128, 2528
44. K. M. Engle, D.-H. Wang, J.-Q. Yu, Angew. Chem. 2010, 122, 6305
45. Angew. Chem. Int. Ed. 2010, 49, 6169.
46. H.-A. Duong, R.-E. Gilligan, M. L.-Cooke, R. J. Phipps, M. J.- Gaunt, Angew. Chem. 2010, DOI:; Angew. Chem. Int. Ed. 2010, DOI:.
47. III catalytic cycle proceeding by electrophilic metalation as it is possible the reactions with and without copper proceed by different mechanisms. For examples of Cu(III)-aryl species, see
48. A. E. King, L. M. Huffman, A. Casitas, M. Costas, X. Ribas, S. Stahl, J. Am. Chem. Soc. 2008, 130, 12068
49. L. M. Huffman, S. Stahl, J. Am. Chem. Soc. 2008, 130, 9196.
50. T. Dohi, M. Ito, N. Yamaoka, K. Morimoto, H. Fujioka, Y. Kita, Tetrahedron 2009, 65, 10797
51. T. Dohi, M. Ito, N. Yamaoka, K. Morimoto, H. Fujioka, Y. Kita, Angew. Chem. 2010, 122, 3406
52. Angew. Chem. Int. Ed. 2010, 49, 3334.
53. D. I. Davies, D. H. Hey, B. Summers, J. Chem. Soc. C 1971, 2681.
54. The arylation could foreseeably proceed by two possible pathways: attack of the electron-rich arene onto the nodal iodine atom of the diaryliodonium salt would form the trivalent iodine intermediate, followed by ligand coupling and rearomatization of the arene nucleophile to form the product; see Refs.-[18] and [19]. Interestingly, although this is a mechanism that is commonly adopted for heteroatom or anionic nucleophiles, the convention associated with reductive elimination should favor transfer of the sterically demanding mesityl group in all cases where the mixed aryl salts are utilized, see Ref.-[20]; however, in no case did we observe this. Therefore, an alternative mechanism may involve the electron-rich arene directly attacking the diaryliodonium salt through an ipso-substitution mechanism, with the desired product formed after rearomatization.
55. R. Koller, K. Stanek, D. Stoltz, Aardoom, R. Aardoom, K. Niedermann, A. Togni, Angew. Chem. 2009, 121, 4396
56. Angew. Chem. Int. Ed. 2009, 48, 4332
57. A. E. Allen, D. W. C. MacMillan, J. Am. Chem. Soc. 2010, 132, 4986
58. H. Xu, S. J. Zuend, M. G. Woll, Y. Tao, E. N. Jacobsen, Science 2010, 327, 986.
59. V. V. Grushin, Acc. Chem. Res. 1992, 25, 529.
60. B. Wang, J. W. Graskemper, L. Qin, S. G. DiMagno, Angew. Chem. 2010, 122, 4173
61. Angew. Chem. Int. Ed. 2010, 49, 4079.