Improved functional group C compatibility in the palladium-catalyzed amination of aryl bromides

Tetrahedron Letters

Volumn 38, Issue 36, 1997, Pages 6359-6362

  Wolfe, John P ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; ANILINE DERIVATIVE; MORPHOLINE DERIVATIVE; PIPERIDINE DERIVATIVE; PYRROLIDINE DERIVATIVE;

AMINATION; ARTICLE; CATALYSIS; DRUG SYNTHESIS; IN VITRO STUDY; REACTION ANALYSIS;

EID: 0030845978     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)01463-9     Document Type: Article

References (19)

1. (a) Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. 1997, 62, 1264-1267 and references cited therein,
2. (b) Louie, J.; Driver, M. S.; Hamann, B. C.; Hartwig, J. F. J. Org. Chem. 1997, 62, 1268-1273 and references cited therein,
3. (c) Wolfe, J. P.; Buchwald, S. L. Manuscript submitted.
4. (d) Marcoux, J-F.; Wagaw, S.; Buchwald, S. L. J. Org. Chem. 1997, 62, 1568-1569.
5. (rac)-PPF-OMe = 1-[2-(Diphenylphosphino)ferrocenyl]ethyl methyl ether. (a) Hayashi, T.; Mise, T.; Fukushima, M.; Kagotani, M.; Nagashima, N.; Hamada, Y.; Matsumoto, A.; Kawakami, S.; Konishi, M.; Yamamoto, K.; Kumada, M. Bull. Chem. Soc. Jpn. 1980, 53, 1138-1151. (b) Togni, A.; Häusel, R. Synlett 1990, 633-635.
6. (rac)-PPF-OMe = 1-[2-(Diphenylphosphino)ferrocenyl]ethyl methyl ether. (a) Hayashi, T.; Mise, T.; Fukushima, M.; Kagotani, M.; Nagashima, N.; Hamada, Y.; Matsumoto, A.; Kawakami, S.; Konishi, M.; Yamamoto, K.; Kumada, M. Bull. Chem. Soc. Jpn. 1980, 53, 1138-1151. (b) Togni, A.; Häusel, R. Synlett 1990, 633-635.
7. Representative Procedure: An oven-dried Schlenk tube was charged with cesium carbonate which had been finely ground with a mortar and pestle (1.4 eq) in a nitrogen-filled glovebox. The tube was capped with a rubber septum and removed from the glovebox. The tube was then charged with Pd2(dba)3 or Pd(OAc)2 and BINAP or PPF-OMe (see Table 1), and purged with argon. The aryl bromide (1.0 eq), the amine (1.2 eq), and toluene (2 mL/mmol halide) were added, and the mixture was heated to 100°C with stirring until the starting material had been consumed as judged by GC analysis. The mixture was cooled to room temperature, diluted with ether (20 mL), filtered, and concentrated. The crude product was then purified by flash chromatography on silica gel. A reaction which employed cesium carbonate that had been finely ground in the air and stored in a dessicator outside of the glovebox gave comparable results to the analogous reaction which employed cesium carbonate from the glovebox.
8. 1H NMR spectra of the material from these sources were identical.
9. Reactions of the enolizable ketone, 4′-bromoacetophenone, were only successful with 4-methylaniline. Attempts to couple this substrate with morpholine or piperidine afforded only low yields (∼15 % by GC) of the desired product.
10. The reaction of 4-bromonitrobenzene with piperidine in DMF in the absence of a palladium catalyst proceeded to completion in 28 h and afforded a 78% isolated yield of N-(4-nitrophenyl)piperidine.
11. 1d. (c) N-(4-nitrophenyl) piperidine (entry 3) and N-(4-cyanophenyl) piperidine (entry 11): Verardo, G.; Giumanini, A. G.; Favret, G.; Strazzolini, P. Synthesis 1991, 447-450. (d) N-(2-carbomethoxyphenyl)-p-anisidine (entry 7): Legrand, L.; Lozac'h, N. Bull. Chem. Soc. Fr. 1969, 1173-1182. (e) N-(4-carboethoxyphenyl) piperidine (entry 8): Khuthier, A-H., Al-Mallah, K. Y.; Hanna, S. Y.; Abdulla, N-A. I. J. Org. Chem. 1987, 52, 1710-1713. (f) N-methyl-N-(4-carboethoxyphenyl) aniline (entry 9): Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901-7902. (g) N-(2,5-xylyl) pyrrolidine (entry 13): Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. In Press. (h) N-(4-methoxyphenyl) morpholine (entry 14): Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. In Press. (i) N-(4-acetylphenyl)-p-toluidine (entry 17): Itier, J.; Casadevall, A. Bull. Chem. Soc. Fr. 1969, 2342-2355. (j) 4-(N-methyl-N-benzyl) aminobenzaldeyde (entry 18): Hora, I. M.; Gupta, V.; Ittyerah, P. I. J. Ind. Chem. Soc. 1972, 49, 901-905.
12. 1d. (c) N-(4-nitrophenyl) piperidine (entry 3) and N-(4-cyanophenyl) piperidine (entry 11): Verardo, G.; Giumanini, A. G.; Favret, G.; Strazzolini, P. Synthesis 1991, 447-450. (d) N-(2-carbomethoxyphenyl)-p-anisidine (entry 7): Legrand, L.; Lozac'h, N. Bull. Chem. Soc. Fr. 1969, 1173-1182. (e) N-(4-carboethoxyphenyl) piperidine (entry 8): Khuthier, A-H., Al-Mallah, K. Y.; Hanna, S. Y.; Abdulla, N-A. I. J. Org. Chem. 1987, 52, 1710-1713. (f) N-methyl-N-(4-carboethoxyphenyl) aniline (entry 9): Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901-7902. (g) N-(2,5-xylyl) pyrrolidine (entry 13): Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. In Press. (h) N-(4-methoxyphenyl) morpholine (entry 14): Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. In Press. (i) N-(4-acetylphenyl)-p-toluidine (entry 17): Itier, J.; Casadevall, A. Bull. Chem. Soc. Fr. 1969, 2342-2355. (j) 4-(N-methyl-N-benzyl) aminobenzaldeyde (entry 18): Hora, I. M.; Gupta, V.; Ittyerah, P. I. J. Ind. Chem. Soc. 1972, 49, 901-905.
13. 1d. (c) N-(4-nitrophenyl) piperidine (entry 3) and N-(4-cyanophenyl) piperidine (entry 11): Verardo, G.; Giumanini, A. G.; Favret, G.; Strazzolini, P. Synthesis 1991, 447-450. (d) N-(2-carbomethoxyphenyl)-p-anisidine (entry 7): Legrand, L.; Lozac'h, N. Bull. Chem. Soc. Fr. 1969, 1173-1182. (e) N-(4-carboethoxyphenyl) piperidine (entry 8): Khuthier, A-H., Al-Mallah, K. Y.; Hanna, S. Y.; Abdulla, N-A. I. J. Org. Chem. 1987, 52, 1710-1713. (f) N-methyl-N-(4-carboethoxyphenyl) aniline (entry 9): Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901-7902. (g) N-(2,5-xylyl) pyrrolidine (entry 13): Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. In Press. (h) N-(4-methoxyphenyl) morpholine (entry 14): Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. In Press. (i) N-(4-acetylphenyl)-p-toluidine (entry 17): Itier, J.; Casadevall, A. Bull. Chem. Soc. Fr. 1969, 2342-2355. (j) 4-(N-methyl-N-benzyl) aminobenzaldeyde (entry 18): Hora, I. M.; Gupta, V.; Ittyerah, P. I. J. Ind. Chem. Soc. 1972, 49, 901-905.
14. 1d. (c) N-(4-nitrophenyl) piperidine (entry 3) and N-(4-cyanophenyl) piperidine (entry 11): Verardo, G.; Giumanini, A. G.; Favret, G.; Strazzolini, P. Synthesis 1991, 447-450. (d) N-(2-carbomethoxyphenyl)-p-anisidine (entry 7): Legrand, L.; Lozac'h, N. Bull. Chem. Soc. Fr. 1969, 1173-1182. (e) N-(4-carboethoxyphenyl) piperidine (entry 8): Khuthier, A-H., Al-Mallah, K. Y.; Hanna, S. Y.; Abdulla, N-A. I. J. Org. Chem. 1987, 52, 1710-1713. (f) N-methyl-N-(4-carboethoxyphenyl) aniline (entry 9): Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901-7902. (g) N-(2,5-xylyl) pyrrolidine (entry 13): Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. In Press. (h) N-(4-methoxyphenyl) morpholine (entry 14): Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. In Press. (i) N-(4-acetylphenyl)-p-toluidine (entry 17): Itier, J.; Casadevall, A. Bull. Chem. Soc. Fr. 1969, 2342-2355. (j) 4-(N-methyl-N-benzyl) aminobenzaldeyde (entry 18): Hora, I. M.; Gupta, V.; Ittyerah, P. I. J. Ind. Chem. Soc. 1972, 49, 901-905.
15. 1d. (c) N-(4-nitrophenyl) piperidine (entry 3) and N-(4-cyanophenyl) piperidine (entry 11): Verardo, G.; Giumanini, A. G.; Favret, G.; Strazzolini, P. Synthesis 1991, 447-450. (d) N-(2-carbomethoxyphenyl)-p-anisidine (entry 7): Legrand, L.; Lozac'h, N. Bull. Chem. Soc. Fr. 1969, 1173-1182. (e) N-(4-carboethoxyphenyl) piperidine (entry 8): Khuthier, A-H., Al-Mallah, K. Y.; Hanna, S. Y.; Abdulla, N-A. I. J. Org. Chem. 1987, 52, 1710-1713. (f) N-methyl-N-(4-carboethoxyphenyl) aniline (entry 9): Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901-7902. (g) N-(2,5-xylyl) pyrrolidine (entry 13): Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. In Press. (h) N-(4-methoxyphenyl) morpholine (entry 14): Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. In Press. (i) N-(4-acetylphenyl)-p-toluidine (entry 17): Itier, J.; Casadevall, A. Bull. Chem. Soc. Fr. 1969, 2342-2355. (j) 4-(N-methyl-N-benzyl) aminobenzaldeyde (entry 18): Hora, I. M.; Gupta, V.; Ittyerah, P. I. J. Ind. Chem. Soc. 1972, 49, 901-905.
16. 1d. (c) N-(4-nitrophenyl) piperidine (entry 3) and N-(4-cyanophenyl) piperidine (entry 11): Verardo, G.; Giumanini, A. G.; Favret, G.; Strazzolini, P. Synthesis 1991, 447-450. (d) N-(2-carbomethoxyphenyl)-p-anisidine (entry 7): Legrand, L.; Lozac'h, N. Bull. Chem. Soc. Fr. 1969, 1173-1182. (e) N-(4-carboethoxyphenyl) piperidine (entry 8): Khuthier, A-H., Al-Mallah, K. Y.; Hanna, S. Y.; Abdulla, N-A. I. J. Org. Chem. 1987, 52, 1710-1713. (f) N-methyl-N-(4-carboethoxyphenyl) aniline (entry 9): Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901-7902. (g) N-(2,5-xylyl) pyrrolidine (entry 13): Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. In Press. (h) N-(4-methoxyphenyl) morpholine (entry 14): Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. In Press. (i) N-(4-acetylphenyl)-p-toluidine (entry 17): Itier, J.; Casadevall, A. Bull. Chem. Soc. Fr. 1969, 2342-2355. (j) 4-(N-methyl-N-benzyl) aminobenzaldeyde (entry 18): Hora, I. M.; Gupta, V.; Ittyerah, P. I. J. Ind. Chem. Soc. 1972, 49, 901-905.
17. 1d. (c) N-(4-nitrophenyl) piperidine (entry 3) and N-(4-cyanophenyl) piperidine (entry 11): Verardo, G.; Giumanini, A. G.; Favret, G.; Strazzolini, P. Synthesis 1991, 447-450. (d) N-(2-carbomethoxyphenyl)-p-anisidine (entry 7): Legrand, L.; Lozac'h, N. Bull. Chem. Soc. Fr. 1969, 1173-1182. (e) N-(4-carboethoxyphenyl) piperidine (entry 8): Khuthier, A-H., Al-Mallah, K. Y.; Hanna, S. Y.; Abdulla, N-A. I. J. Org. Chem. 1987, 52, 1710-1713. (f) N-methyl-N-(4-carboethoxyphenyl) aniline (entry 9): Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901-7902. (g) N-(2,5-xylyl) pyrrolidine (entry 13): Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. In Press. (h) N-(4-methoxyphenyl) morpholine (entry 14): Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. In Press. (i) N-(4-acetylphenyl)-p-toluidine (entry 17): Itier, J.; Casadevall, A. Bull. Chem. Soc. Fr. 1969, 2342-2355. (j) 4-(N-methyl-N-benzyl) aminobenzaldeyde (entry 18): Hora, I. M.; Gupta, V.; Ittyerah, P. I. J. Ind. Chem. Soc. 1972, 49, 901-905.
18. 1d. (c) N-(4-nitrophenyl) piperidine (entry 3) and N-(4-cyanophenyl) piperidine (entry 11): Verardo, G.; Giumanini, A. G.; Favret, G.; Strazzolini, P. Synthesis 1991, 447-450. (d) N-(2-carbomethoxyphenyl)-p-anisidine (entry 7): Legrand, L.; Lozac'h, N. Bull. Chem. Soc. Fr. 1969, 1173-1182. (e) N-(4-carboethoxyphenyl) piperidine (entry 8): Khuthier, A-H., Al-Mallah, K. Y.; Hanna, S. Y.; Abdulla, N-A. I. J. Org. Chem. 1987, 52, 1710-1713. (f) N-methyl-N-(4-carboethoxyphenyl) aniline (entry 9): Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901-7902. (g) N-(2,5-xylyl) pyrrolidine (entry 13): Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. In Press. (h) N-(4-methoxyphenyl) morpholine (entry 14): Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. In Press. (i) N-(4-acetylphenyl)-p-toluidine (entry 17): Itier, J.; Casadevall, A. Bull. Chem. Soc. Fr. 1969, 2342-2355. (j) 4-(N-methyl-N-benzyl) aminobenzaldeyde (entry 18): Hora, I. M.; Gupta, V.; Ittyerah, P. I. J. Ind. Chem. Soc. 1972, 49, 901-905.
19. 1d. (c) N-(4-nitrophenyl) piperidine (entry 3) and N-(4-cyanophenyl) piperidine (entry 11): Verardo, G.; Giumanini, A. G.; Favret, G.; Strazzolini, P. Synthesis 1991, 447-450. (d) N-(2-carbomethoxyphenyl)-p-anisidine (entry 7): Legrand, L.; Lozac'h, N. Bull. Chem. Soc. Fr. 1969, 1173-1182. (e) N-(4-carboethoxyphenyl) piperidine (entry 8): Khuthier, A-H., Al-Mallah, K. Y.; Hanna, S. Y.; Abdulla, N-A. I. J. Org. Chem. 1987, 52, 1710-1713. (f) N-methyl-N-(4-carboethoxyphenyl) aniline (entry 9): Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901-7902. (g) N-(2,5-xylyl) pyrrolidine (entry 13): Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. In Press. (h) N-(4-methoxyphenyl) morpholine (entry 14): Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. In Press. (i) N-(4-acetylphenyl)-p-toluidine (entry 17): Itier, J.; Casadevall, A. Bull. Chem. Soc. Fr. 1969, 2342-2355. (j) 4-(N-methyl-N-benzyl) aminobenzaldeyde (entry 18): Hora, I. M.; Gupta, V.; Ittyerah, P. I. J. Ind. Chem. Soc. 1972, 49, 901-905.