Efficient iridium-catalyzed C-H functionalization/silylation of heteroarenes

Angewandte Chemie - International Edition

Volumn 47, Issue 39, 2008, Pages 7508-7510

  Lu, Biao ^a   Falck, John R ^a  

^a UNIVERSITY OF TEXAS SOUTHWESTERN MEDICAL CENTER   (United States)

Author keywords

C H activation; Heterocycles; Iridium; Silanes

Indexed keywords

SILANES;

C-H ACTIVATION; CYCLOOCTADIENE; HETEROARENES; HETEROCYCLES; NORBORNENE; SILYLATION;

IRIDIUM;

CARBON; HYDROGEN; INDOLE DERIVATIVE; IRIDIUM; SILANE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY;

CARBON; CATALYSIS; HYDROGEN; INDOLES; IRIDIUM; MOLECULAR STRUCTURE; SILANES;

EID: 54749090359     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200802456     Document Type: Article

References (44)

1. Recent examples: a) S. E. Denmark, R. F. Sweis in Metal-Catalyzed Cross-Coupling Reaction s, Vol. 1, 2nd ed. (Eds.: A. De Meijere, F. Diederich), Wiley-VCH, Weinheim, 2004, pp. 163-216;
2. b) Y. Nakao, A. K. Sahoo, H. Imanaka, A. Yada, T. Hiyama, Pure Appl. Chem. 2006, 78, 435;
3. c) K. Suzawa, M. Ueno, A. E. H. Wheatley, Y. Kondo, Chem. Commun. 2006, 4850;
4. d) P. Pierrat, P. Gros, Y. Fort, Org. Lett. 2005, 7, 697;
5. e) E. Abele, E. Lukevics, Heterocycles 2002, 57, 361.
6. a) D. Bai, S. Han, Z.-H. Lu, S. Wang, Can. J. Chem. 2008, 86, 230;
7. b) T. Kumagai, S. Itsuno, Macromolecules 2002, 35, 5323.
8. A. K. Franz, Curr. Opin. Drug Discovery Dev. 2007, 10, 654.
9. a) T.-H. Nguyen, A.-S. Castanet, J. Mortier, Org. Lett. 2006, 8, 765;
10. b) C. G. Hartung, A. Fecher, B. Chapell, V. Snieckus, Org. Lett. 2003, 5, 1899.
11. a) S. Denmark, J. M. Kallemeyn, Org. Lett. 2003, 5, 3483;
12. b) E. McNeill, T. E. Barder, S. L. Buchwald, Org. Lett. 2007, 9, 3785;
13. c) A. Hamze, O. Provot, M. Alami, J.-D. Brion, Org. Lett. 2006, 8, 931.
14. a) R. G. Bergman, Nature 2007, 446, 39;
15. b) I. V. Seregin, V. Gevorgyan, Chem. Soc. Rev. 2007, 36, 1173;
16. c) K. Godula, D. Sames, Science 2006, 312, 67;
17. d) A. R. Dick, M. S. Sanford, Tetrahedron 2006, 62, 2439;
18. e) F. Kakiuchi in Handbook of C-H Transformations, Vol. 1 (Ed.: G. Dyker), Wiley-VCH, Weinheim, 2005, pp. 131-137, 265-266.
19. Ru catalysis: a) F. Kakiuchi, K. Tsuchiya, M. Matsumoto, E. Mizushima, N. Chatani, J. Am. Chem. Soc. 2004, 126, 12792;
20. b) F. Kakiuchi, M. Matsumoto, K. Tsuchiya, K. Igi, T. Hayamizu, N. Chatani, S. Murai, J. Organomet. Chem. 2003, 686, 134;
21. c) F. Kakiuchi, K. Igi, M. Matsumoto, T. Hayamizu, N. Chatani, S. Murai, Chem. Lett. 2002, 396.
22. Pt catalysis: a) M. Murata, N. Fukuyama, J.-I. Wada, S. Watanabe, Y. Masyda, Chem. Lett. 2007, 36, 910;
23. b) N. Tsukada, J. F. Hartwig, J. Am. Chem. Soc. 2005, 127, 5022;
24. c) Y. Uchimaru, A. M. M. El Sayed, M. Tanaka, Organometallics 1993, 12, 2065.
25. Ir catalysis: a) T. Saiki, Y. Nishio, T. Ishiyama, N. Miyaura, Organometallics 2006, 25, 6068;
26. b) T. Ishiyama, K. Sato, Y. Nishio, N. Miyaura, Angew. Chem. 2003, 115, 5504;
27. Angew. Chem. Int. Ed. 2003, 42, 5346.
28. H.-J. Borschberg, Curr. Org. Chem. 2005, 9, 1465.
29. a) D. R. Stuart, K. Fagnou, Science 2007, 316, 1172;
30. b) N. R. Deprez, D. Kalyani, A. Krause, M. S. Sanford, J. Am. Chem. Soc. 2006, 128, 4972;
31. c) N. P. Grimster, C. Gauntlett, C. R. A. Godfrey, M. J. Gaunt, Angew. Chem. 2005, 117, 3185;
32. Angew. Chem. Int. Ed. 2005, 44, 3125;
33. d) E. M. Ferreira, B. M. Stoltz, J. Am. Chem. Soc. 2003, 125, 9578.
34. a) S. Paul, G. A. Chotana, D. Holmes, R. Reichle, P. E. Maleczka, M. R. Smith, J. Am. Chem. Soc. 2006, 128, 15552;
35. b) T. M. Boller, J. M. Murphy, M. Hapke, T. Ishiyama, N. Miyaura, J. F. Hartwig, J. Am. Chem. Soc. 2005, 127, 14263;
36. c) T. Ishiyama, Y. Nobuta, J. F. Hartwig, N. Miyaura, Chem. Commun. 2003, 2924;
37. d) T. Ishiyama, N. Miyaura, Pure Appl. Chem. 2006, 78, 1369.
38. T. Ishiyama, K. Sata, Y. Nishio, T. Saiki, N. Miyaura, Chem. Commun. 2005, 5065.
39. Alternative synthesis of 2-triethylsilylindole: K. Kamikawa, S. Kinoshita, M. Furusyo, S. Takemoto, H. Matsuzaka, M. Uemura, J. Org. Chem. 2007, 72, 3394.
40. Other unsaturated molecules, e.g., tetramethylethylene, 1-hexene, 1-heptyne, and diisopropyl azodicarboxylate, had no effect on the yield of 2.
41. For prior use of 2-norbornene in catalytic C-H activations, see references [7a and c]. The exact role of 2-norbornene as a promoter of the iridium-catalyzed reactions reported herein is unclear. The identification of norbornane, by GC-MS methods, in the reaction mixture suggests it functions as a sink for the hydrogen generated during the reaction. Additionally, it may play a more intimate role as a participant in the catalytic cycle. We speculate the bicyclic skeleton of norbornene affords greater steric shielding or stability towards unproductive β-hydride eliminations than comparable iridium complexes with cyclic or acyclic olefins. Unfortunately, attempts to detect Ir-norbornene intermediates by NMR methods were disappointing.
42. 2]/4,4-di- tert-butyl-2,2-bipyridine, produced little, if any, 2.
43. 3SiH increased from 1.5 to 4.0.
44. Tamao-Kumada-Fleming oxidation review: R. J. Mullins, S. L. Jolley, A. R. Knapp in Name Reactions for Functional Group Transformations (Eds.: J. J. Li, E. J. Corey), Wiley, Hoboken, 2007, pp. 237-247.