Copper-catalyzed cross-couplings with part-per-million catalyst loadings

Angewandte Chemie - International Edition

Volumn 48, Issue 31, 2009, Pages 5691-5693

  Larsson, Per Fredrik ^a   Correa, Arkaitz ^b   Carril, Monica ^b   Norrby, Per Ola ^a   Bolm, Carsten ^b  

^a UNIVERSITY OF GOTHENBURG   (Sweden)

^b RWTH AACHEN UNIVERSITY   (Germany)

Author keywords

Capper; Cross coupling; Homogeneous catalysis; N arylation; Ullmann reaction

Indexed keywords

CAPPER; CROSS-COUPLING; HOMOGENEOUS CATALYSIS; N-ARYLATION; ULLMANN REACTION;

AROMATIC COMPOUNDS; REACTION KINETICS;

CATALYSIS;

CATION; COPPER; PHENYLIODONIUM; PYRAZOLE; PYRAZOLE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMISTRY;

CATALYSIS; COPPER; ONIUM COMPOUNDS; PYRAZOLES;

EID: 70349929617     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200902236     Document Type: Article

References (77)

1. a) Metal-Catalyzed Cross-Coupling Reactions (Eds.: A. de Meijere, F. Diederich), 2nd ed., Wiley-VCH, Weinheim, 2004;
2. b) J.-P. Corbet, G. Mignani, Chem. Rev. 2006, 106, 2651;
3. c) D. S. Surry, S. L. Buchwald, Angew. Chem. 2008, 120, 6438;
4. Angew. Chem. Int. Ed. 2008, 47, 6338.
5. Reviews: a) S. V. Ley, A. W. Thomas, Angew. Chem. 2003, 115, 5558;
6. Angew. Chem. Int. Ed. 2003, 42, 5400;
7. b) K. Kunz, U. Scholz, D. Ganzer, Synlett 2003, 2428;
8. c) I. P. Beletskaya, A. V. Cheprakov, Coord. Chem. Rev. 2004, 248, 2337;
9. d) J.-P. Corbet, G. Mignani, Chem. Rev. 2006, 106, 2651;
10. e) M. Carril, R. SanMartin, E. Domínguez, Chem. Soc. Rev. 2008, 37, 639;
11. f) F. Monnier, M. Taillefer, Angew. Chem. 2008, 120, 3140;
12. Angew. Chem. Int. Ed. 2008, 47, 3096;
13. g) D. Ma, Q. Cai, Acc. Chem. Res. 2008, 41, 1450;
14. h) G. Evano, N. Blanchard, M. Toumi, Chem. Rev. 2008, 108, 3054.
15. a) F. Ullmann, Ber. Dtsch. Chem. Ges. 1903, 36, 2382;
16. b) F. Ullmann, Ber. Dtsch. Chem. Ges. 1904, 37, 853;
17. c) F. Ullmann, P. Sponagel, Ber. Dtsch. Chem. Ges. 1905, 38, 2211;
18. d) I. Goldberg, Ber. Dtsch. Chem. Ges. 1906, 39, 1691.
19. For selected examples of Ullmann type cross-couplings with N-, O-, S- and C-nucleophiles involving metal salt/ligand combinations, see: a) J. C. Antilla, A. Klapars, S. L. Buchwald, J. Am. Chem. Soc. 2002, 124, 11684;
20. b) J. C. Antilla, J. M. Bassin, T. E. Barder, S. L. Buchwald, J. Org. Chem. 2004, 69, 5578;
21. c) F. Y. Kwong, S. L. Buchwald, Org. Lett. 2003, 5, 793;
22. d) H.-J. Cristau, P. P. Cellier, J.-F. Spindler, M. Taillefer, Chem. Eur. J. 2004, 10, 5607;
23. e) L. Xu, D. Zhu, F. Wu, R. Wang, B. Wan, Tetrahedron 2005, 61, 6533;
24. f) Z. Zhang, J. Mao, D. Zhu, F. Wu, H. Chen, B. Wan, Tetrahedron 2006, 62, 4435;
25. g) H. Rao, Y. Jin, H. Fu, Y. Jiang, Y. Zhao, Chem. Eur. J. 2006, 12, 3636;
26. h) A. Ouali, R. Laurent, A.-M. Caminade, J.-P. Majoral, M. Taillefer, J. Am. Chem. Soc. 2006, 128, 15990;
27. i) L. Zhu, L. Cheng, Y. Zhang, R. Xie, J. You, J. Org. Chem. 2007, 72, 2737;
28. j) D. Jiang, H. Fu, Y. Jiang, Y. Zhao, J. Org. Chem. 2007, 72, 672;
29. k) A. Shafir, S. L. Buchwald, J. Am. Chem. Soc. 2006, 128, 8742;
30. l) B. de Lange, M. H. Lambers-Verstappen, L. Schmieder-van de Vondervoort, N. Sereinig, R. de Rijk, A. H. M. de Vries, J. G. de Vries, Synlett 2006, 3105;
31. m) X. Lv, W. Bao, J. Org. Chem. 2007, 72, 3863;
32. n) R. A. Altman, E. D. Koval, S. L. Buchwald, J. Org. Chem. 2007, 72, 6190;
33. o) F. Monnier, F. Turtaut, L. Duroure, M. Taillefer, Org. Lett. 2008, 10, 3203.
34. For cross-couplings catalyzed by less than 1 mol % of copper, see: a) F. Lang, D. Zewge, I. N. Houpis, R. P. Volante, Tetrahedron Lett. 2001, 42, 3251;
35. b) M. Kuil, E. K. Bekedam, G. M. Visser, A. van den Hoogenband, J. W Terpstra, P. C. J. Kamer, P. W N. M. van Leeuwen, G. P. F. van Strijdonck, Tetrahedron Lett. 2005, 46, 2405.
36. To the best of our knowledge, the phrase "homeopathic dose" was first used by Beletskaya and Cheprakov in the context of palladium-catalyzed Heck reactions with very low catalyst loadings. Later, de Vries, Reetz, and co-workers used it for ligand-free palladium catalyses with catalyst loadings in the range of 0.01-0.1 mol%. For key references, see: a) I. P. Beletskaya, A. V. Cheprakov, Chem. Rev. 2000, 100, 3009;
37. b) A. H. M. de Vries, J. M. C. A. Mulders, J. H. M. Mommers, H. J. W Henderickx, J. G. de Vries, Org. Lett. 2003, 5, 3285;
38. c) A. H. M. de Vries, J. G. de Vries, Eur. J. Org. Chem. 2003, 799;
39. d) M. T. Reetz, J. G. de Vries, Chem. Commun. 2004, 1559;
40. e) J. G. de Vries, Dalton Trans. 2006, 421, and references therein.
41. a) A. Correa, C. Bolm, Angew. Chem. 2007, 119, 9018;
42. Angew. Chem. Int. Ed. 2007, 46, 8862;
43. b) A. Correa, C. Bolm, Adv. Synth. Catal. 2008, 350, 391;
44. c) A. Correa, S. Elmore, C. Bolm, Chem. Eur. J. 2008, 14, 3527;
45. d) O. Bistri, A. Correa, C. Bolm, Angew. Chem. 2008, 120, 596;
46. Angew. Chem. Int. Ed. 2008, 47, 586;
47. e) J. Bonnamour, C. Bolm, Org. Lett. 2008, 10, 2665;
48. f) A. Correa, M. Carril, C. Bolm, Angew. Chem. 2008, 120, 2922;
49. Angew. Chem. Int. Ed. 2008, 47, 2880;
50. g) M. Carril, A. Correa, C. Bolm, Angew. Chem. 2008, 120, 4940;
51. Angew. Chem. Int. Ed. 2008, 47, 4862;
52. h) A. Correa, M. Carril, C. Bolm, Chem. Eur. J. 2008, 14, 10919.
53. 3 were recently reported for reactions run in water under otherwise identical conditions: Y.-C. Teo, Adv. Synth. Catal. 2009, 351, 720.
54. 3 is important. See: G. Cahiez, V. Habiak, C. Duplais, A. Moyeux, Angew. Chem. 2007, 119, 4442;
55. Angew. Chem. Int. Ed. 2007, 46, 4364.
56. For a Correspondence on that issue, see: S. L. Buchwald, C. Bolm, Angew. Chem. 2009, 121, 5694;
57. Angew. Chem. Int. Ed. 2009, 48, 5586.
58. a) M. Taillefer, N. Xia, A. Oualli, Angew. Chem. 2007, 119, 952;
59. Angew. Chem. Int. Ed. 2007, 46, 934;
60. b) R.-J. Song, C.-L. Deng, Y.-X. Xie, J.-H. Li, Tetrahedron Lett. 2007, 48, 7845;
61. c) Z. Wang, H. Fu, Y. Jiang, Y. Zhao, Synlett 2008, 2540;
62. d) C. M. Rao Volla, P. Vogel, Tetrahedron Lett. 2008, 49, 5961;
63. e) J. Mao, G. Xie, M. Wu, J. Guo, S. Ji, Adv. Synth. Catal. 2008, 350, 2477;
64. f) H. Huang, H. Jiang, K. Chen, H. Liu, J. Org. Chem. 2008, 73, 9061;
65. g) X. Ku, H. Huang, H. Jiang, H. Liu, J. Comb. Chem. 2009, 11, 338;
66. h) S. Li, W. Jia, N. Jiao, Adv. Synth. Catal. 2009, 351, 569.
67. 2O had been applied. Control experiments indicated that in most cases the yields were superior with the latter.
68. Due to the sensitivity of the reaction towards metal traces it was necessary to either use new equipment (glassware, stir-bar etc.) each time or to wash used vials with KOH/isopropyl alcohol followed by rinsing with distilled water and drying overnight at 150°C in order to entirely suppress the formation of 3 by metal traces from previous reactions.
69. 3 in toluene at 80°C.
70. For an excellent Highlight providing additional insight into the importance of trace metals in catalyzed Sonogashira reactions, see: H. Plenio, Angew. Chem. 2008, 120, 7060;
71. Angew. Chem. Int. Ed. 2008, 47, 6954.
72. Based on results from other experiments in combination with substrate analyses by atom absorption spectroscopy we conclude that palladium is most likely catalytically irrelevant under the conditions reported here. For findings relating to microwave-accelerated Suzuki couplings and related reactions with "homeopathic" quantities of palladium, see: a) R. K. Arvela, N. E. Leadbeater, M. S. Sangi, V. A. Williams, P. Granados, R. D. Singer, J. Org. Chem. 2005, 70, 161;
73. b) A. Alimardanov, L. Schmieder-van de Vondervoort, A. H. M. de Vries, J. G. de Vries, Adv. Synth. Catal. 2004, 346, 1812;
74. c) S. A. Weissman, D. Zewge, C. Chen, J. Org. Chem. 2005, 70, 1508.
75. For comparison and in relation to our earlier work (refs. [7] and [9]), all reactions were also performed under iron catalysis. In those reactions, for example, carbazole and pyrrole could not be arylated at all, whereas the yields in the phenylations of butyramide and acetanilide (78 and 75%, respectively) were superior to those observed in the copper catalyses.
76. For recent mechanistic studies on copper-catalyzed N-arylations, see: a) E. R. Strieter, B. Bhayana, S. L. Buchwald, J. Am. Chem. Soc. 2009, 131, 78;
77. b) J. W Tye, Z. Weng, A. M. Johns, C. D. Incarvito, J. F. Hartwig, J. Am. Chem. Soc. 2008, 130, 9971.