Palladium-catalyzed synthesis of N-aryl-2-benzylindolines via tandem arylation of 2-allylaniline: Control of selectivity through in situ catalyst modification

Journal of the American Chemical Society

Volumn 126, Issue 43, 2004, Pages 13906-13907

  Lira, Ricardo ^a   Wolfe, John P ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANILINE DERIVATIVE; BENZENE DERIVATIVE; CARBON; NITROGEN; PALLADIUM COMPLEX;

ARTICLE; ARYLATION; CATALYSIS; CHELATION; CHEMICAL BOND; CHEMICAL REACTION; ELECTRON; REACTION TIME; SUBSTITUTION REACTION; SYNTHESIS;

EID: 7444269099     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0460920     Document Type: Article

References (43)

1. For recent examples, see: (a) Ajamian, A.; Gleason, J. L. Angew. Chem., Int. Ed. 2004, 43, 3754. (b) Yamamoto, Y.; Nakagai, Y.; Itoh, K. Chem. Eur. J. 2004, 10, 231. (c) Cossy, J.; Bargiggia, F.; BouzBouz, S. Org. Lett. 2003, 5, 459. (d) Thadani, A. N.; Rawal, V. H. Org. Lett. 2002, 4, 4317. (e) Son, S. U.; Park, K. H.; Chung, Y. K. J. Am. Chem. Soc. 2002, 124, 6838. (f) Louie, J.; Bielawski, C. W.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 11312. (g) Evans, P. A.; Robinson, J. E. J. Am. Chem. Soc. 2001, 123, 4609.
2. For recent examples, see: (a) Ajamian, A.; Gleason, J. L. Angew. Chem., Int. Ed. 2004, 43, 3754. (b) Yamamoto, Y.; Nakagai, Y.; Itoh, K. Chem. Eur. J. 2004, 10, 231. (c) Cossy, J.; Bargiggia, F.; BouzBouz, S. Org. Lett. 2003, 5, 459. (d) Thadani, A. N.; Rawal, V. H. Org. Lett. 2002, 4, 4317. (e) Son, S. U.; Park, K. H.; Chung, Y. K. J. Am. Chem. Soc. 2002, 124, 6838. (f) Louie, J.; Bielawski, C. W.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 11312. (g) Evans, P. A.; Robinson, J. E. J. Am. Chem. Soc. 2001, 123, 4609.
3. For recent examples, see: (a) Ajamian, A.; Gleason, J. L. Angew. Chem., Int. Ed. 2004, 43, 3754. (b) Yamamoto, Y.; Nakagai, Y.; Itoh, K. Chem. Eur. J. 2004, 10, 231. (c) Cossy, J.; Bargiggia, F.; BouzBouz, S. Org. Lett. 2003, 5, 459. (d) Thadani, A. N.; Rawal, V. H. Org. Lett. 2002, 4, 4317. (e) Son, S. U.; Park, K. H.; Chung, Y. K. J. Am. Chem. Soc. 2002, 124, 6838. (f) Louie, J.; Bielawski, C. W.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 11312. (g) Evans, P. A.; Robinson, J. E. J. Am. Chem. Soc. 2001, 123, 4609.
4. For recent examples, see: (a) Ajamian, A.; Gleason, J. L. Angew. Chem., Int. Ed. 2004, 43, 3754. (b) Yamamoto, Y.; Nakagai, Y.; Itoh, K. Chem. Eur. J. 2004, 10, 231. (c) Cossy, J.; Bargiggia, F.; BouzBouz, S. Org. Lett. 2003, 5, 459. (d) Thadani, A. N.; Rawal, V. H. Org. Lett. 2002, 4, 4317. (e) Son, S. U.; Park, K. H.; Chung, Y. K. J. Am. Chem. Soc. 2002, 124, 6838. (f) Louie, J.; Bielawski, C. W.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 11312. (g) Evans, P. A.; Robinson, J. E. J. Am. Chem. Soc. 2001, 123, 4609.
5. For recent examples, see: (a) Ajamian, A.; Gleason, J. L. Angew. Chem., Int. Ed. 2004, 43, 3754. (b) Yamamoto, Y.; Nakagai, Y.; Itoh, K. Chem. Eur. J. 2004, 10, 231. (c) Cossy, J.; Bargiggia, F.; BouzBouz, S. Org. Lett. 2003, 5, 459. (d) Thadani, A. N.; Rawal, V. H. Org. Lett. 2002, 4, 4317. (e) Son, S. U.; Park, K. H.; Chung, Y. K. J. Am. Chem. Soc. 2002, 124, 6838. (f) Louie, J.; Bielawski, C. W.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 11312. (g) Evans, P. A.; Robinson, J. E. J. Am. Chem. Soc. 2001, 123, 4609.
6. For recent examples, see: (a) Ajamian, A.; Gleason, J. L. Angew. Chem., Int. Ed. 2004, 43, 3754. (b) Yamamoto, Y.; Nakagai, Y.; Itoh, K. Chem. Eur. J. 2004, 10, 231. (c) Cossy, J.; Bargiggia, F.; BouzBouz, S. Org. Lett. 2003, 5, 459. (d) Thadani, A. N.; Rawal, V. H. Org. Lett. 2002, 4, 4317. (e) Son, S. U.; Park, K. H.; Chung, Y. K. J. Am. Chem. Soc. 2002, 124, 6838. (f) Louie, J.; Bielawski, C. W.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 11312. (g) Evans, P. A.; Robinson, J. E. J. Am. Chem. Soc. 2001, 123, 4609.
7. For recent examples, see: (a) Ajamian, A.; Gleason, J. L. Angew. Chem., Int. Ed. 2004, 43, 3754. (b) Yamamoto, Y.; Nakagai, Y.; Itoh, K. Chem. Eur. J. 2004, 10, 231. (c) Cossy, J.; Bargiggia, F.; BouzBouz, S. Org. Lett. 2003, 5, 459. (d) Thadani, A. N.; Rawal, V. H. Org. Lett. 2002, 4, 4317. (e) Son, S. U.; Park, K. H.; Chung, Y. K. J. Am. Chem. Soc. 2002, 124, 6838. (f) Louie, J.; Bielawski, C. W.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 11312. (g) Evans, P. A.; Robinson, J. E. J. Am. Chem. Soc. 2001, 123, 4609.
8. (a) Kim, W.-G.; Kim, J.-P.; Koshino, H.; Shin-Ya, K.; Seto, H.; Yoo, I.-D. Tetrahedron 1997, 53, 4309.
9. (b) Matsuoka, H.; Kato, N.; Ohi, N.; Miyamoto, K.; Mihara, M.; Takeda, Y. Chem. Pharm. Bull. 1997, 45, 1146.
10. (a) Nicolaou, K. C.; Roecker, A. J.; Hughes, R.; van Summeren, R.; Pfefferkorn, J. A.; Winssinger, N. Bioorg. Med. Chem. 2003, 11, 465.
11. (b) Nicolaou, K. C.; Roecker, A. J.; Pfefferkorn, J. A.; Cao, G.-Q. J. Am. Chem. Soc. 2000, 122, 2966.
12. (c) Bytschkov, I.; Siebeneicher, H.; Doye, S. Eur. J. Org. Chem. 2003, 2888.
13. (a) Muci, A. R.; Buchwald, S. L Top. Curr. Chem. 2002, 219, 131.
14. (b) Hartwig, J. F. Pure Appl. Chem. 1999, 71, 1417.
15. For the synthesis of heterocycles from γ-hydroxy or -aminoalkenes and aryl bromides, see: (a) Ney, J. E.; Wolfe, J. P. Angew. Chem., Int. Ed. 2004, 43, 3605. (b) Wolfe, J. P.; Rossi, M. A. J. Am. Chem. Soc. 2004, 126, 1620.
16. For the synthesis of heterocycles from γ-hydroxy or -aminoalkenes and aryl bromides, see: (a) Ney, J. E.; Wolfe, J. P. Angew. Chem., Int. Ed. 2004, 43, 3605. (b) Wolfe, J. P.; Rossi, M. A. J. Am. Chem. Soc. 2004, 126, 1620.
17. For transformations of 2-allylanilines to indolines, indoles, or oxindoles see: (a) Reference 3. (b) Clive, D. J. L.; Farina, V.; Singh, A.; Wong, C. K.; Kiel, W. A.; Menchen, S. M. J. Org. Chem. 1980, 45, 2120. (c) Danishefsky, S.; Berman, E. M.; Ciufolini, M.; Etheredge, S. J.; Segmuller, B. E. J. Am. Chem. Soc. 1985, 107, 3891. (d) Gagné, M. R.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 4108. (e) Benali, O.; Miranda, M. A.; Tormos, R. Eur. J. Org. Chem. 2002, 2317. (f) Hegedus, L. S.; Allen, G. F.; Bozell, J. J.; Waterman, E. L. J. Am. Chem. Soc. 1978, 100, 5800. (g) El Ali, B.; Okuro, K.; Vasapollo, G.; Alper, H. J. Am. Chem. Soc. 1996, 118, 4264. (h) Larock, R. C.; Hightower, T. R.; Hasvold, L. A.; Peterson, K. P. J. Org. Chem. 1996, 61, 3584.
18. For transformations of 2-allylanilines to indolines, indoles, or oxindoles see: (a) Reference 3. (b) Clive, D. J. L.; Farina, V.; Singh, A.; Wong, C. K.; Kiel, W. A.; Menchen, S. M. J. Org. Chem. 1980, 45, 2120. (c) Danishefsky, S.; Berman, E. M.; Ciufolini, M.; Etheredge, S. J.; Segmuller, B. E. J. Am. Chem. Soc. 1985, 107, 3891. (d) Gagné, M. R.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 4108. (e) Benali, O.; Miranda, M. A.; Tormos, R. Eur. J. Org. Chem. 2002, 2317. (f) Hegedus, L. S.; Allen, G. F.; Bozell, J. J.; Waterman, E. L. J. Am. Chem. Soc. 1978, 100, 5800. (g) El Ali, B.; Okuro, K.; Vasapollo, G.; Alper, H. J. Am. Chem. Soc. 1996, 118, 4264. (h) Larock, R. C.; Hightower, T. R.; Hasvold, L. A.; Peterson, K. P. J. Org. Chem. 1996, 61, 3584.
19. For transformations of 2-allylanilines to indolines, indoles, or oxindoles see: (a) Reference 3. (b) Clive, D. J. L.; Farina, V.; Singh, A.; Wong, C. K.; Kiel, W. A.; Menchen, S. M. J. Org. Chem. 1980, 45, 2120. (c) Danishefsky, S.; Berman, E. M.; Ciufolini, M.; Etheredge, S. J.; Segmuller, B. E. J. Am. Chem. Soc. 1985, 107, 3891. (d) Gagné, M. R.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 4108. (e) Benali, O.; Miranda, M. A.; Tormos, R. Eur. J. Org. Chem. 2002, 2317. (f) Hegedus, L. S.; Allen, G. F.; Bozell, J. J.; Waterman, E. L. J. Am. Chem. Soc. 1978, 100, 5800. (g) El Ali, B.; Okuro, K.; Vasapollo, G.; Alper, H. J. Am. Chem. Soc. 1996, 118, 4264. (h) Larock, R. C.; Hightower, T. R.; Hasvold, L. A.; Peterson, K. P. J. Org. Chem. 1996, 61, 3584.
20. For transformations of 2-allylanilines to indolines, indoles, or oxindoles see: (a) Reference 3. (b) Clive, D. J. L.; Farina, V.; Singh, A.; Wong, C. K.; Kiel, W. A.; Menchen, S. M. J. Org. Chem. 1980, 45, 2120. (c) Danishefsky, S.; Berman, E. M.; Ciufolini, M.; Etheredge, S. J.; Segmuller, B. E. J. Am. Chem. Soc. 1985, 107, 3891. (d) Gagné, M. R.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 4108. (e) Benali, O.; Miranda, M. A.; Tormos, R. Eur. J. Org. Chem. 2002, 2317. (f) Hegedus, L. S.; Allen, G. F.; Bozell, J. J.; Waterman, E. L. J. Am. Chem. Soc. 1978, 100, 5800. (g) El Ali, B.; Okuro, K.; Vasapollo, G.; Alper, H. J. Am. Chem. Soc. 1996, 118, 4264. (h) Larock, R. C.; Hightower, T. R.; Hasvold, L. A.; Peterson, K. P. J. Org. Chem. 1996, 61, 3584.
21. For transformations of 2-allylanilines to indolines, indoles, or oxindoles see: (a) Reference 3. (b) Clive, D. J. L.; Farina, V.; Singh, A.; Wong, C. K.; Kiel, W. A.; Menchen, S. M. J. Org. Chem. 1980, 45, 2120. (c) Danishefsky, S.; Berman, E. M.; Ciufolini, M.; Etheredge, S. J.; Segmuller, B. E. J. Am. Chem. Soc. 1985, 107, 3891. (d) Gagné, M. R.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 4108. (e) Benali, O.; Miranda, M. A.; Tormos, R. Eur. J. Org. Chem. 2002, 2317. (f) Hegedus, L. S.; Allen, G. F.; Bozell, J. J.; Waterman, E. L. J. Am. Chem. Soc. 1978, 100, 5800. (g) El Ali, B.; Okuro, K.; Vasapollo, G.; Alper, H. J. Am. Chem. Soc. 1996, 118, 4264. (h) Larock, R. C.; Hightower, T. R.; Hasvold, L. A.; Peterson, K. P. J. Org. Chem. 1996, 61, 3584.
22. For transformations of 2-allylanilines to indolines, indoles, or oxindoles see: (a) Reference 3. (b) Clive, D. J. L.; Farina, V.; Singh, A.; Wong, C. K.; Kiel, W. A.; Menchen, S. M. J. Org. Chem. 1980, 45, 2120. (c) Danishefsky, S.; Berman, E. M.; Ciufolini, M.; Etheredge, S. J.; Segmuller, B. E. J. Am. Chem. Soc. 1985, 107, 3891. (d) Gagné, M. R.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 4108. (e) Benali, O.; Miranda, M. A.; Tormos, R. Eur. J. Org. Chem. 2002, 2317. (f) Hegedus, L. S.; Allen, G. F.; Bozell, J. J.; Waterman, E. L. J. Am. Chem. Soc. 1978, 100, 5800. (g) El Ali, B.; Okuro, K.; Vasapollo, G.; Alper, H. J. Am. Chem. Soc. 1996, 118, 4264. (h) Larock, R. C.; Hightower, T. R.; Hasvold, L. A.; Peterson, K. P. J. Org. Chem. 1996, 61, 3584.
23. For transformations of 2-allylanilines to indolines, indoles, or oxindoles see: (a) Reference 3. (b) Clive, D. J. L.; Farina, V.; Singh, A.; Wong, C. K.; Kiel, W. A.; Menchen, S. M. J. Org. Chem. 1980, 45, 2120. (c) Danishefsky, S.; Berman, E. M.; Ciufolini, M.; Etheredge, S. J.; Segmuller, B. E. J. Am. Chem. Soc. 1985, 107, 3891. (d) Gagné, M. R.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 4108. (e) Benali, O.; Miranda, M. A.; Tormos, R. Eur. J. Org. Chem. 2002, 2317. (f) Hegedus, L. S.; Allen, G. F.; Bozell, J. J.; Waterman, E. L. J. Am. Chem. Soc. 1978, 100, 5800. (g) El Ali, B.; Okuro, K.; Vasapollo, G.; Alper, H. J. Am. Chem. Soc. 1996, 118, 4264. (h) Larock, R. C.; Hightower, T. R.; Hasvold, L. A.; Peterson, K. P. J. Org. Chem. 1996, 61, 3584.
24. For transformations of 2-allylanilines to indolines, indoles, or oxindoles see: (a) Reference 3. (b) Clive, D. J. L.; Farina, V.; Singh, A.; Wong, C. K.; Kiel, W. A.; Menchen, S. M. J. Org. Chem. 1980, 45, 2120. (c) Danishefsky, S.; Berman, E. M.; Ciufolini, M.; Etheredge, S. J.; Segmuller, B. E. J. Am. Chem. Soc. 1985, 107, 3891. (d) Gagné, M. R.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 4108. (e) Benali, O.; Miranda, M. A.; Tormos, R. Eur. J. Org. Chem. 2002, 2317. (f) Hegedus, L. S.; Allen, G. F.; Bozell, J. J.; Waterman, E. L. J. Am. Chem. Soc. 1978, 100, 5800. (g) El Ali, B.; Okuro, K.; Vasapollo, G.; Alper, H. J. Am. Chem. Soc. 1996, 118, 4264. (h) Larock, R. C.; Hightower, T. R.; Hasvold, L. A.; Peterson, K. P. J. Org. Chem. 1996, 61, 3584.
25. For syntheses of indoles from 2-vinyl- or 2-alkynylanilines, see: (a) Larock, R. C.; Pace, P.; Yang, H.; Russell, C. E.; Cacchi, S.; Fabrizi, G. Tetrahedron 1998, 54, 9961. (b) Cacchi, S.; Fabrizi, G.; Pace, P. J. Org. Chem. 1998, 63, 1001. (c) Larock, R. C.; Yum, E. K. J. Am. Chem. Soc. 1991, 113, 6689.
26. For syntheses of indoles from 2-vinyl- or 2-alkynylanilines, see: (a) Larock, R. C.; Pace, P.; Yang, H.; Russell, C. E.; Cacchi, S.; Fabrizi, G. Tetrahedron 1998, 54, 9961. (b) Cacchi, S.; Fabrizi, G.; Pace, P. J. Org. Chem. 1998, 63, 1001. (c) Larock, R. C.; Yum, E. K. J. Am. Chem. Soc. 1991, 113, 6689.
27. For syntheses of indoles from 2-vinyl- or 2-alkynylanilines, see: (a) Larock, R. C.; Pace, P.; Yang, H.; Russell, C. E.; Cacchi, S.; Fabrizi, G. Tetrahedron 1998, 54, 9961. (b) Cacchi, S.; Fabrizi, G.; Pace, P. J. Org. Chem. 1998, 63, 1001. (c) Larock, R. C.; Yum, E. K. J. Am. Chem. Soc. 1991, 113, 6689.
28. dpe-phos = bis(2-diphenylphosphinophenyl)ether. Xantphos = 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene.
29. N-(4-Methoxyphenyl)-2-methylindole was also isolated in 24% yield. This side product may arise from β-hydride elimination/isomerization of 9 due to relatively slow reductive elimination of the more electron-rich arylpalladium complex. See: Culkin, D. A.; Hartwig, J. F. Organometallics 2004, 23, 3398.
30. Decreasing the reaction temperature to 70°C failed to increase the selectivity for monoarylation.
31. Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158.
32. For sequential N,N-diarylation of aniline derivatives, see: (a) Thayumanavan, S.; Barlow, S.; Marder, S. R. Chem. Mater. 1997, 9, 3231. (b) Harris, M. C.; Buchwald, S. L. J. Org. Chem. 2000, 65, 5327. (c) Harris, M. C.; Geis, O.; Buchwald, S. L. J. Org. Chem. 1999, 64, 6019.
33. For sequential N,N-diarylation of aniline derivatives, see: (a) Thayumanavan, S.; Barlow, S.; Marder, S. R. Chem. Mater. 1997, 9, 3231. (b) Harris, M. C.; Buchwald, S. L. J. Org. Chem. 2000, 65, 5327. (c) Harris, M. C.; Geis, O.; Buchwald, S. L. J. Org. Chem. 1999, 64, 6019.
34. For sequential N,N-diarylation of aniline derivatives, see: (a) Thayumanavan, S.; Barlow, S.; Marder, S. R. Chem. Mater. 1997, 9, 3231. (b) Harris, M. C.; Buchwald, S. L. J. Org. Chem. 2000, 65, 5327. (c) Harris, M. C.; Geis, O.; Buchwald, S. L. J. Org. Chem. 1999, 64, 6019.
35. 3/4 catalyst system in reactions of γ-(N-arylamino)-alkenes with aryl halides afforded exclusively N,N-diarylated products. See ref 5a.
36. A complex mixture of N,N-diarylated- and N-monoarylated olefin isomers was generated along with a small amount of 3.
37. Four-coordinate arylpalladium amido complexes undergo C-N bond-forming reductive elimination more slowly than three-coordinate complexes. See: Yamashita, M.; Hartwig, J. F. J. Am. Chem. Soc. 2004, 126, 5344.
38. The reaction was monitored by GC analysis, and the N-arylation was found to be complete and essentially quantitative after 30 min at 80°C.
39. (a) Boncella, J. M.; Villanueva, L. A. J. Organomet. Chem. 1994, 465, 297.
40. (b) Villanueva, L. A.; Abboud, K. A.; Boncella, J. M. Organometallics 1992, 11, 2963.
41. (c) Helaja, J.; Göttlich, R. J. Chem. Soc., Chem. Commun. 2002, 120.
42. (d) Tsutsui, H.; Narasaka, K. Chem. Lett. 1999, 45
43. Milstein, D.; Stille, J. K. J. Am. Chem. Soc. 1979, 101, 4981.