The First Rapid Palladium-Catalyzed Aminations of (Azahetero)aryl Chlorides under Temperature-Controlled Microwave Heating

Synlett

Volumn , Issue 12, 2003, Pages 1822-1825

  Maes, Bert U W ^a   Loones, Kristof T J ^a   Lemière, Guy L F ^a   Dommisse, Roger A ^a  

^a UNIVERSITY OF ANTWERP   (Belgium)

Author keywords

Aryl chlorides; Buchwald Hartwig amination; Homogeneous catalysis; Microwave irradiation; Palladium

Indexed keywords

CHLORIDE; PALLADIUM; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE;

AMINATION; ARTICLE; CATALYSIS; HEATING; MICROWAVE RADIATION; TEMPERATURE DEPENDENCE;

EID: 0142123943     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2003-41475     Document Type: Article

References (48)

1. For recent reviews and books on microwave-assisted organic synthesis including examples of microwave-accelerated palladium-catalyzed reactions see: (a) Lidström, P.; Tierney, J.; Wathey, B.; Westman, J. Tetrahedron 2001, 57, 9225. (b) Larhed, M.; Hallberg, A. Drug Discov. Today 2001, 6, 406. (c) Larhed, M.; Moberg, C.; Hallberg, A. Acc. Chem. Res. 2002, 35, 717. (d) Lew, A. ; Krutzik, P. O.; Hart, M. E.; Chamberlin, A. R. J. Comb. Chem. 2002, 4, 95. (e) Hayes, B. L. Microwave Synthesis: Chemistry at the Speed of Light; CEM Publishing: Matthews, 2002.
2. For recent reviews and books on microwave-assisted organic synthesis including examples of microwave- accelerated palladium-catalyzed reactions see: (a) Lidström, P.; Tierney, J.; Wathey, B.; Westman, J. Tetrahedron 2001, 57, 9225. (b) Larhed, M.; Hallberg, A. Drug Discov. Today 2001, 6, 406. (c) Larhed, M.; Moberg, C.; Hallberg, A. Acc. Chem. Res. 2002, 35, 717. (d) Lew, A. ; Krutzik, P. O.; Hart, M. E.; Chamberlin, A. R. J. Comb. Chem. 2002, 4, 95. (e) Hayes, B. L. Microwave Synthesis: Chemistry at the Speed of Light; CEM Publishing: Matthews, 2002.
3. For recent reviews and books on microwave-assisted organic synthesis including examples of microwave- accelerated palladium-catalyzed reactions see: (a) Lidström, P.; Tierney, J.; Wathey, B.; Westman, J. Tetrahedron 2001, 57, 9225. (b) Larhed, M.; Hallberg, A. Drug Discov. Today 2001, 6, 406. (c) Larhed, M.; Moberg, C.; Hallberg, A. Acc. Chem. Res. 2002, 35, 717. (d) Lew, A. ; Krutzik, P. O.; Hart, M. E.; Chamberlin, A. R. J. Comb. Chem. 2002, 4, 95. (e) Hayes, B. L. Microwave Synthesis: Chemistry at the Speed of Light; CEM Publishing: Matthews, 2002.
4. For recent reviews and books on microwave-assisted organic synthesis including examples of microwave- accelerated palladium-catalyzed reactions see: (a) Lidström, P.; Tierney, J.; Wathey, B.; Westman, J. Tetrahedron 2001, 57, 9225. (b) Larhed, M.; Hallberg, A. Drug Discov. Today 2001, 6, 406. (c) Larhed, M.; Moberg, C.; Hallberg, A. Acc. Chem. Res. 2002, 35, 717. (d) Lew, A. ; Krutzik, P. O.; Hart, M. E.; Chamberlin, A. R. J. Comb. Chem. 2002, 4, 95. (e) Hayes, B. L. Microwave Synthesis: Chemistry at the Speed of Light; CEM Publishing: Matthews, 2002.
5. For recent reviews and books on microwave-assisted organic synthesis including examples of microwave- accelerated palladium-catalyzed reactions see: (a) Lidström, P.; Tierney, J.; Wathey, B.; Westman, J. Tetrahedron 2001, 57, 9225. (b) Larhed, M.; Hallberg, A. Drug Discov. Today 2001, 6, 406. (c) Larhed, M.; Moberg, C.; Hallberg, A. Acc. Chem. Res. 2002, 35, 717. (d) Lew, A. ; Krutzik, P. O.; Hart, M. E.; Chamberlin, A. R. J. Comb. Chem. 2002, 4, 95. (e) Hayes, B. L. Microwave Synthesis: Chemistry at the Speed of Light; CEM Publishing: Matthews, 2002.
6. Czarnik, A. W. Acc. Chem. Res. 1996, 29, 112.
7. For reviews on the Buchwald-Hartwig reaction see: (a) Barañano, D. ; Mann, G.; Hartwig, J. F. Curr. Org. Chem. 1997, 1, 287. (b) Frost, C. G.; Mendonça, P. J. Chem. Soc., Perkin Trans. 1 1998, 2615. (c) Hartwig, J. F. Angew. Chem. Int. Ed. 1998, 37, 2046. (d) Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999, 576, 125. (e) Hartwig, J. F. In Modern Amination Methods; Ricci, A., Ed.; Wiley-VCH: Weinheim, 2000. (f) Muci, A. R.; Buchwald, S. L. Top. Curr. Chem. 2002, 219, 131.
8. For reviews on the Buchwald-Hartwig reaction see: (a) Barañano, D. ; Mann, G.; Hartwig, J. F. Curr. Org. Chem. 1997, 1, 287. (b) Frost, C. G.; Mendonça, P. J. Chem. Soc., Perkin Trans. 1 1998, 2615. (c) Hartwig, J. F. Angew. Chem. Int. Ed. 1998, 37, 2046. (d) Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999, 576, 125. (e) Hartwig, J. F. In Modern Amination Methods; Ricci, A., Ed.; Wiley-VCH: Weinheim, 2000. (f) Muci, A. R.; Buchwald, S. L. Top. Curr. Chem. 2002, 219, 131.
9. For reviews on the Buchwald-Hartwig reaction see: (a) Barañano, D. ; Mann, G.; Hartwig, J. F. Curr. Org. Chem. 1997, 1, 287. (b) Frost, C. G.; Mendonça, P. J. Chem. Soc., Perkin Trans. 1 1998, 2615. (c) Hartwig, J. F. Angew. Chem. Int. Ed. 1998, 37, 2046. (d) Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999, 576, 125. (e) Hartwig, J. F. In Modern Amination Methods; Ricci, A., Ed.; Wiley-VCH: Weinheim, 2000. (f) Muci, A. R.; Buchwald, S. L. Top. Curr. Chem. 2002, 219, 131.
10. For reviews on the Buchwald-Hartwig reaction see: (a) Barañano, D. ; Mann, G.; Hartwig, J. F. Curr. Org. Chem. 1997, 1, 287. (b) Frost, C. G.; Mendonça, P. J. Chem. Soc., Perkin Trans. 1 1998, 2615. (c) Hartwig, J. F. Angew. Chem. Int. Ed. 1998, 37, 2046. (d) Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999, 576, 125. (e) Hartwig, J. F. In Modern Amination Methods; Ricci, A., Ed.; Wiley-VCH: Weinheim, 2000. (f) Muci, A. R.; Buchwald, S. L. Top. Curr. Chem. 2002, 219, 131.
11. For reviews on the Buchwald-Hartwig reaction see: (a) Barañano, D. ; Mann, G.; Hartwig, J. F. Curr. Org. Chem. 1997, 1, 287. (b) Frost, C. G.; Mendonça, P. J. Chem. Soc., Perkin Trans. 1 1998, 2615. (c) Hartwig, J. F. Angew. Chem. Int. Ed. 1998, 37, 2046. (d) Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999, 576, 125. (e) Hartwig, J. F. In Modern Amination Methods; Ricci, A., Ed.; Wiley-VCH: Weinheim, 2000. (f) Muci, A. R.; Buchwald, S. L. Top. Curr. Chem. 2002, 219, 131.
12. For reviews on the Buchwald-Hartwig reaction see: (a) Barañano, D. ; Mann, G.; Hartwig, J. F. Curr. Org. Chem. 1997, 1, 287. (b) Frost, C. G.; Mendonça, P. J. Chem. Soc., Perkin Trans. 1 1998, 2615. (c) Hartwig, J. F. Angew. Chem. Int. Ed. 1998, 37, 2046. (d) Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999, 576, 125. (e) Hartwig, J. F. In Modern Amination Methods; Ricci, A., Ed.; Wiley-VCH: Weinheim, 2000. (f) Muci, A. R.; Buchwald, S. L. Top. Curr. Chem. 2002, 219, 131.
13. For a recent review dealing with palladium-catalyzed coupling reactions of aryl chlorides see: Littke, A. F.; Fu, G. C. Angew. Chem. Int. Ed. 2002, 41, 4176.
14. (a) For the first Buchwald-Hartwig amination of an activated aryl chloride see: Beller, M.; Riermeier, T. H.; Reisinger, C-P.; Hermann, W. A. Tetrahedron Lett. 1997, 38, 2073.
15. (b) The first example of a Buchwald-Hartwig amination of an activated azaheteroaryl chloride (2-chloropyridine) was already reported in 1996: Wagaw, S.; Buchwald, S. L. J. Org. Chem. 1996, 61, 7240.
16. For the first Buchwald-Hartwig amination of an unactivated aryl chloride see: Reddy, N. P.; Tanaka, M. Tetrahedron Lett. 1997, 38, 4807.
17. For palladium-catalyzed animations of aryl chlorides using catalysts based on bulky and electron rich phosphane ligands see: (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998. 120, 7369. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 720, 9722. (c) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (d) Hartwig, J. F.; Kawatsura, M. ; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (f) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 1237. (g) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. Organometallics 1999, 18, 1840. (h) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (i) For a combination of a palladacycle and a secondary phosphane as ligand see: Schnyder, A.; Indolese, A. F.; Studer, M.; Blaser, H.-U. Angew. Chem. Int. Ed. 2002, 41, 3668. (j) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int. Ed. 2002, 41, 4746. (k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553.
18. For palladium-catalyzed animations of aryl chlorides using catalysts based on bulky and electron rich phosphane ligands see: (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998. 120, 7369. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 720, 9722. (c) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (d) Hartwig, J. F.; Kawatsura, M. ; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (f) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 1237. (g) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. Organometallics 1999, 18, 1840. (h) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (i) For a combination of a palladacycle and a secondary phosphane as ligand see: Schnyder, A.; Indolese, A. F.; Studer, M.; Blaser, H.-U. Angew. Chem. Int. Ed. 2002, 41, 3668. (j) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int. Ed. 2002, 41, 4746. (k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553.
19. For palladium-catalyzed animations of aryl chlorides using catalysts based on bulky and electron rich phosphane ligands see: (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998. 120, 7369. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 720, 9722. (c) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (d) Hartwig, J. F.; Kawatsura, M. ; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (f) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 1237. (g) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. Organometallics 1999, 18, 1840. (h) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (i) For a combination of a palladacycle and a secondary phosphane as ligand see: Schnyder, A.; Indolese, A. F.; Studer, M.; Blaser, H.-U. Angew. Chem. Int. Ed. 2002, 41, 3668. (j) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int. Ed. 2002, 41, 4746. (k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553.
20. For palladium-catalyzed animations of aryl chlorides using catalysts based on bulky and electron rich phosphane ligands see: (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998. 120, 7369. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 720, 9722. (c) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (d) Hartwig, J. F.; Kawatsura, M. ; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (f) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 1237. (g) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. Organometallics 1999, 18, 1840. (h) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (i) For a combination of a palladacycle and a secondary phosphane as ligand see: Schnyder, A.; Indolese, A. F.; Studer, M.; Blaser, H.-U. Angew. Chem. Int. Ed. 2002, 41, 3668. (j) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int. Ed. 2002, 41, 4746. (k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553.
21. For palladium-catalyzed animations of aryl chlorides using catalysts based on bulky and electron rich phosphane ligands see: (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998. 120, 7369. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 720, 9722. (c) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (d) Hartwig, J. F.; Kawatsura, M. ; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (f) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 1237. (g) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. Organometallics 1999, 18, 1840. (h) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (i) For a combination of a palladacycle and a secondary phosphane as ligand see: Schnyder, A.; Indolese, A. F.; Studer, M.; Blaser, H.-U. Angew. Chem. Int. Ed. 2002, 41, 3668. (j) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int. Ed. 2002, 41, 4746. (k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553.
22. For palladium-catalyzed animations of aryl chlorides using catalysts based on bulky and electron rich phosphane ligands see: (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998. 120, 7369. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 720, 9722. (c) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (d) Hartwig, J. F.; Kawatsura, M. ; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (f) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 1237. ( g) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. Organometallics 1999, 18, 1840. (h) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (i) For a combination of a palladacycle and a secondary phosphane as ligand see: Schnyder, A.; Indolese, A. F.; Studer, M.; Blaser, H.-U. Angew. Chem. Int. Ed. 2002, 41, 3668. (j) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int. Ed. 2002, 41, 4746. (k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553.
23. For palladium-catalyzed animations of aryl chlorides using catalysts based on bulky and electron rich phosphane ligands see: (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998. 120, 7369. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 720, 9722. (c) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (d) Hartwig, J. F.; Kawatsura, M. ; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (f) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 1237. (g) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. Organometallics 1999, 18, 1840. (h) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (i) For a combination of a palladacycle and a secondary phosphane as ligand see: Schnyder, A.; Indolese, A. F.; Studer, M.; Blaser, H.-U. Angew. Chem. Int. Ed. 2002, 41, 3668. (j) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int. Ed. 2002, 41, 4746. (k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553.
24. For palladium-catalyzed animations of aryl chlorides using catalysts based on bulky and electron rich phosphane ligands see: (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998. 120, 7369. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 720, 9722. (c) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (d) Hartwig, J. F.; Kawatsura, M. ; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (f) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 1237. (g) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. Organometallics 1999, 18, 1840. (h) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (i) For a combination of a palladacycle and a secondary phosphane as ligand see: Schnyder, A.; Indolese, A. F.; Studer, M.; Blaser, H.-U. Angew. Chem. Int. Ed. 2002, 41, 3668. (j) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int. Ed. 2002, 41, 4746. (k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553.
25. For palladium-catalyzed animations of aryl chlorides using catalysts based on bulky and electron rich phosphane ligands see: (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998. 120, 7369. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 720, 9722. (c) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (d) Hartwig, J. F.; Kawatsura, M. ; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (f) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 1237. (g) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. Organometallics 1999, 18, 1840. (h) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (i) For a combination of a palladacycle and a secondary phosphane as ligand see: Schnyder, A.; Indolese, A. F.; Studer, M.; Blaser, H.-U. Angew. Chem. Int. Ed. 2002, 41, 3668. (j) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int. Ed. 2002, 41, 4746. (k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553.
26. For palladium-catalyzed animations of aryl chlorides using catalysts based on bulky and electron rich phosphane ligands see: (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998. 120, 7369. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 720, 9722. (c) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (d) Hartwig, J. F.; Kawatsura, M. ; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (f) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 1237. (g) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. Organometallics 1999, 18, 1840. (h) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (i) For a combination of a palladacycle and a secondary phosphane as ligand see: Schnyder, A.; Indolese, A. F.; Studer, M.; Blaser, H.-U. Angew. Chem. Int. Ed. 2002, 41, 3668. (j) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int. Ed. 2002, 41, 4746. (k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553.
27. For palladium-catalyzed animations of aryl chlorides using catalysts based on bulky and electron rich phosphane ligands see: (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998. 120, 7369. (b) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 720, 9722. (c) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (d) Hartwig, J. F.; Kawatsura, M. ; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (f) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 1237. (g) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. Organometallics 1999, 18, 1840. (h) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (i) For a combination of a palladacycle and a secondary phosphane as ligand see: Schnyder, A.; Indolese, A. F.; Studer, M.; Blaser, H.-U. Angew. Chem. Int. Ed. 2002, 41, 3668. (j) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int. Ed. 2002, 41, 4746. (k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553.
28. For palladium-catalyzed aminations of aryl chlorides using catalysts based on bulky and electron rich carbene ligands see: (a) Huang, J.; Grasa, G.; Nolan, S. P. Org. Lett. 1999, 1, 1307. (b) Stauffer, S. R.; Lee, S.; Stambuli, J. P.; Hauck, S. I.; Hartwig, J. F. Org. Lett. 2000, 2, 1423. (c) Titcomb, L. R.; Caddick, S.; Cloke, F. G. N.; Wilson, D. J.; McKerrecher, D. Chem. Commun. 2001, 1388.
29. For palladium-catalyzed aminations of aryl chlorides using catalysts based on bulky and electron rich carbene ligands see: (a) Huang, J.; Grasa, G.; Nolan, S. P. Org. Lett. 1999, 1, 1307. (b) Stauffer, S. R.; Lee, S.; Stambuli, J. P.; Hauck, S. I.; Hartwig, J. F. Org. Lett. 2000, 2, 1423. (c) Titcomb, L. R.; Caddick, S.; Cloke, F. G. N.; Wilson, D. J.; McKerrecher, D. Chem. Commun. 2001, 1388.
30. For palladium-catalyzed aminations of aryl chlorides using catalysts based on bulky and electron rich carbene ligands see: (a) Huang, J.; Grasa, G.; Nolan, S. P. Org. Lett. 1999, 1, 1307. (b) Stauffer, S. R.; Lee, S.; Stambuli, J. P.; Hauck, S. I.; Hartwig, J. F. Org. Lett. 2000, 2, 1423. (c) Titcomb, L. R.; Caddick, S.; Cloke, F. G. N.; Wilson, D. J.; McKerrecher, D. Chem. Commun. 2001, 1388.
31. 7j). Although, other catalysts have also been used to perform Buchwald-Hartwig aminations at r.t. the scope is generally broader at higher temperature. Moreover, the reaction times for couplings at r.t. are in the order of hours to 1 d (see refs. 7h, 8b).
32. For microwave-assisted palladium-catalyzed amination of bromobenzenes and 2-bromonaphthalene see: (a) Sharifi, A.; Hosseinzadeh, R.; Mirzaei, M. Monatsh. Chem. 2002, 133, 329. (b) Wan, Y.; Alterman, M.; Hallberg, A. Synthesis 2002, 1597. (c) For microwave-assisted palladium-catalyzed amination of 1-bromonaphthalenes and 5- and 8- bromoquinolines see: Wang, T.; Magnin, D. R.; Hamann, L. G. Org. Lett. 2003, 5, 897.
33. For microwave-assisted palladium-catalyzed amination of bromobenzenes and 2-bromonaphthalene see: (a) Sharifi, A.; Hosseinzadeh, R.; Mirzaei, M. Monatsh. Chem. 2002, 133, 329. (b) Wan, Y.; Alterman, M.; Hallberg, A. Synthesis 2002, 1597. (c) For microwave-assisted palladium-catalyzed amination of 1-bromonaphthalenes and 5- and 8- bromoquinolines see: Wang, T.; Magnin, D. R.; Hamann, L. G. Org. Lett. 2003, 5, 897.
34. For microwave-assisted palladium-catalyzed amination of bromobenzenes and 2-bromonaphthalene see: (a) Sharifi, A.; Hosseinzadeh, R.; Mirzaei, M. Monatsh. Chem. 2002, 133, 329. (b) Wan, Y.; Alterman, M.; Hallberg, A. Synthesis 2002, 1597. (c) For microwave-assisted palladium-catalyzed amination of 1-bromonaphthalenes and 5- and 8-bromoquinolines see: Wang, T.; Magnin, D. R.; Hamann, L. G. Org. Lett. 2003, 5, 897.
35. Diarylamines are considered as 'privileged structures': single molecular frameworks, able to provide ligands for diverse receptors: (a) Evans, B. E.; Rittle, K. E.; Bock, M. G.; Dipardo, R. M.; Freidinger, R. M.; Whitter, W. L.; Lundell, G. F.; Veber, D. F.; Anderson, P. S.; Chang, R. S. L.; Lotti, V. J.; Cerino, D. J.; Chen, T. B.; Kling, P. J.; Kunkel, K. A.; Springer, J. P.; Hirshfield, J. J. Med. Chem. 1988, 31, 2235. (b) Ariëns, E. J.; Beld, A. J.; Rodrigues de Miranda, J. F.; Simonis, A. M. In The Receptors a Comprehensive Treatise; O'Brien, R. D., Ed.; Plenum Press: New York, 1979.
36. Diarylamines are considered as 'privileged structures': single molecular frameworks, able to provide ligands for diverse receptors: (a) Evans, B. E.; Rittle, K. E.; Bock, M. G.; Dipardo, R. M.; Freidinger, R. M.; Whitter, W. L.; Lundell, G. F.; Veber, D. F.; Anderson, P. S.; Chang, R. S. L.; Lotti, V. J.; Cerino, D. J.; Chen, T. B.; Kling, P. J.; Kunkel, K. A.; Springer, J. P.; Hirshfield, J. J. Med. Chem. 1988, 31, 2235. (b) Ariëns, E. J.; Beld, A. J.; Rodrigues de Miranda, J. F.; Simonis, A. M. In The Receptors a Comprehensive Treatise; O'Brien, R. D., Ed.; Plenum Press: New York, 1979.
37. (a) Košmrlj, J.; Maes, B. U. W.; Lemière, G. L. F.; Haemers, A. Synlett 2000, 1581.
38. (b) Jonckers, T. H. M.; Maes, B. U. W.; Lemière, G. L. F.; Dommisse, R. Tetrahedron 2001, 57, 7027.
39. (c) Maes, B. U. W.; Loones, K. T. J.; Jonckers, T. H. M.; Lemière, G. L. F.; Dommisse, R. A.; Haemers, A. Synlett 2002, 1995.
40. (d) Jonckers, T. H. M.; Maes, B. U. W.; Lemière, G. L. F.; Rombouts, G.; Pieters, L.; Haemers, A.; Dommisse, R. A. Synlett 2003, 615.
41. 7h).
42. In this preliminary study no attempts were made to further reduce the catalyst loading.
43. Since primary anilines are known to give diarylation we used a larger excess of aniline (1.5 equiv instead of 1.2 equiv) to suppress the formation of such an undesired compound. MS analysis of the crude reaction mixtures of the aminations with p-toluidine revealed in every case a peak with a mass that is in accordance with the presence of diarylated p-toluidine (Table 1, entries 4, 6, 10 and 11). Since only small amounts of diarylated p-toluidine were formed no attempts were made to isolate these side compounds.
44. 17 However, also in this case a tremendous increase in conversion rate was observed under microwave irradiation (speed-up factor: 132). See ref. 7h.
45. The reaction of 3-chloropyridine with N-methylaniline and 2-chloropyridine with morpholine was performed at a double concentration in comparison with the classical heating experiments reported by Buchwald due to the size limitation of the pressure vials and the high temperatures used (150°C or 200°C).
46. 2O. The filtrate was subsequently evaporated under reduced pressure and the residue purified by flash column chromatography on silica gel.
47. NAr reaction works the best: For the coupling of p-toluidine with 2-chloropyridine an isolated yield of only 10% of N-(2-pyridyl)-4-methylaniline was obtained, which proves that the uncatalyzed pathway is not very important under the conditions studied.
48. Temperature, pressure and power curves as function of the reaction time for the microwave-assisted coupling of 3-chloropyridine with N-methylaniline (Table 1, entry 3) (Figure 1). Table presented.