Palladium-catalyzed intermolecular alkenylation of indoles by solvent-controlled regioselective C-H functionalization

Angewandte Chemie - International Edition

Volumn 44, Issue 20, 2005, Pages 3125-3129

  Grimster, Neil P ^a   Gauntlett, Carolyn ^a   Godfrey, Christopher R A ^b   Gaunt, Matthew J ^a  

^a UNIVERSITY OF CAMBRIDGE   (United Kingdom)

^b SYNGENTA CROP PROTECTION AG   (Switzerland)

Author keywords

C C coupling; Heck reaction; Indoles; Palladium; Regioselectivity

Indexed keywords

ACETIC ACID; CATALYSIS; MOLECULAR DYNAMICS; NITROGEN COMPOUNDS; OXIDATION; SOLVENTS;

BISALKENYLATED; C-H FUNCTIONALIZATION; INDOLES; INTERMOLECULAR ALKENYLATION;

PALLADIUM COMPOUNDS;

EID: 18844405201     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200500468     Document Type: Article

References (35)

1. For recent reviews, see: a) A. B. Dounay, L. E. Overman, Chem. Rev. 2003, 103, 2945;
2. b) I. P. Beletskaya, A. V. Cheprakov, Chem. Rev. 2000, 100, 3009;
3. c) A. de Meijere, F. E. Meyer, Angew. Chem. 1994, 106, 2473;
4. Angew. Chem. Int. Ed. Engl. 1994, 34, 2379.
5. a) I. Moritani, Y. Fujiwara, Tetrahedron Lett. 1967, 1119;
6. b) Y. Fujiwara, I. Moritani, S. Danno, R. Asano, S. Teranishi, J. Am. Chem. Soc. 1969, 91, 7166;
7. for a recent intramolecular application of this reaction, see: c) H. Zhang, E. M. Ferreira, B. M. Stoltz, Angew. Chem. 2004, 116, 6270;
8. Angew. Chem. Int. Ed. 2004, 43, 6144, and references therein.
9. The term C-H functionalization is used in a general sense to describe the activation and transformation of a C-H bond. This term was described by Sames and co-workers; see: a) B. Sezen, D. Sames, J. Am. Chem. Soc. 2003, 125, 10580;
10. see also: b) A. E. Shilov, G. B. Shul'pin, Chem. Rev. 1997, 97, 2879;
11. c) V. Ritleng, C. Sirlin, M. Preffer, Chem. Rev. 2002, 102, 1731;
12. d) G. Dyker, Angew. Chem. 1999, 111, 1808;
13. Angew. Chem. Int. Ed. 1999, 38, 1698.
14. a) R. J. Sundberg, Indoles, Academic Press, New York, 1996;
15. b) L. S. Hegedus, Angew. Chem. 1988, 100, 1147;
16. Angew. Chem. Int. Ed. 1988, 27, 1113;
17. c) G. W. Gribble, J. Chem. Soc. Perkin Trans, 1 2000, 1045;
18. for a recent metal-catalyzed synthesis of indoles, see: d) M. C. Willis, G. N. Brace, I. P. Holmes, Angew. Chem. 2005, 117, 407;
19. Angew. Chem. Int. Ed. 2005, 44, 403.
20. For examples of the palladium-catalyzed intramolecular C-H functionalization of indoles, see: a) E. M. Ferreira, B. M. Stoltz, J. Am. Chem. Soc. 2003, 125, 9578;
21. b) C. Liu, X. Han, X. Wang, R. A. Widenhoefer, J. Am. Chem. Soc. 2004, 126, 3700;
22. c) G. Abbiati, E. M. Becalli, G. Broggini, C. Zoni, J. Org. Chem. 2003, 68, 7625;
23. for direct palladium-catalyzed arylation reactions, see: d) B. Sezen, D. Sames, J. Am. Chem. Soc. 2003, 125, 5274;
24. e) B. S. Lane, D. Sames, Org. Lett. 2004, 6, 2897;
25. for a gold-catalyzed coupling reaction, see: f) A. Arcadi, G. Bianchi, M. Chiarini, G. D'Anniballe, F. Marinelli, Synlett 2004, 944;
26. for a stoichiometric palladium-catalyzed alkenylation, see: g) T. Itahara, M. Ikeda, T. Sakakibara, J. Chem. Soc. Perkin Trans, 1 1983, 1361.
27. J. Chengguo, W. Lu, T. Kitamura, Y. Fujiwara, Org. Lett. 1999, 1, 2097.
28. During the preparation of this manuscript we became aware of a report relating to a C2 alkenylation of an indole that contains a metal-directing group on the indole nitrogen atom: E. Capito, J. M. Brown, A. Ricci, Chem. Commun. 2005, in press.
29. a) R. J. Sundberg, The Chemistry of Indoles, Academic Press, New York, 1970, pp. 78-83;
30. b) A. H. Jackson, B. Naidoo, P. Smith, Tetrahedron 1968, 24, 6119.
31. For an overview of oxidative palladium-catalyzed transformations, see: M. S. Sigman, M. Schultz, J. Org. Biomol. Chem. 2004, 2, 2551.
32. a) B. A. Steinhoff, S. R. Fix, S. S. Stahl, J. Am. Chem. Soc. 2002, 124, 766;
33. b) for an effect of DMSO, see: M. S. Chen, C. M. White, J. Am. Chem. Soc. 2004, 126, 1346.
34. Conditions reported by Ferreira and Stoltz (reference [5a]) for an intramolecular process gave 2a in 34% yield.
35. For a recent example of Pd migrations, see: M. A. Campo, Q. Huang, T. Yoa, Q. Tian, R. C. Larock, J. Am. Chem. Soc. 2003, 125, 11507.