Expanding Pd-catalyzed C-N bond-forming processes: The first amidation of aryl sulfonates, aqueous amination, and complementarity with Cu-catalyzed reactions

Journal of the American Chemical Society

Volumn 125, Issue 22, 2003, Pages 6653-6655

  Huang, Xiaohua ^a   Anderson, Kevin W ^a   Zim, Danilo ^a   Jiang, Lei ^a   Klapars, Artis ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENESULFONIC ACID DERIVATIVE; CARBON; COPPER; NITROGEN; PALLADIUM; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; SULFONIC ACID DERIVATIVE;

AMIDATION; AMINATION; AQUEOUS SOLUTION; ARTICLE; CATALYSIS; CHEMICAL BINDING; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; COMPLEX FORMATION; METAL BINDING; REACTION ANALYSIS;

AMIDES; AMINATION; AMINES; ARYLSULFONATES; BENZENE DERIVATIVES; CATALYSIS; COPPER;

EID: 0038579438     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja035483w     Document Type: Article

References (23)

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4. 2 could offer a partial solution to this problem, this was both experimentally complicated and still had a fairly narrow substrate scope (e.g., no primary aliphatic amines, no acyclic secondary amines): Harris, M. C.; Huang, X.; Buchwald, S. L. Org. Lett. 2002, 4, 2885.
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7. (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998, 120, 7369. (b) Hartwig, J. F.; Hamann, B. C. U.S. Patent 6,235,938, 2001. Ni-catalyzed coupling of sulfoximines with aryl tosylates: (c) Bolm, C.; Hildebrand, J. P.; Rudolph, J. Synthesis 2000, 911.
8. (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998, 120, 7369. (b) Hartwig, J. F.; Hamann, B. C. U.S. Patent 6,235,938, 2001. Ni-catalyzed coupling of sulfoximines with aryl tosylates: (c) Bolm, C.; Hildebrand, J. P.; Rudolph, J. Synthesis 2000, 911.
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10. Ligand 1 is commercially available from Strem Chemical. (a) Kaye, S.; Fox, J. M.; Hicks, F. A.; Buchwald, S. L. Adv. Synth. Catal. 2001, 343, 789. (b) Tomori, M.; Fox, J. M.; Buchwald, S. L. J. Org. Chem. 2000, 65, 5334.
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12. Only a few examples of the coupling of amides with aryl triflates have been disclosed, cf.: Yin, J.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 6043.
13. For a Pd-catalyzed oxidation reaction accelerated by t-BuOH as a cosolvent, see: Bagdanoff, J. T.; Ferreira, E. M.; Stolz, B. M. Org. Lett. 2003, 5, 835.
14. In preliminary experiments, primary and secondary alcohols provided poor results while tert-amyl alcohol was a suitable solvent.
15. Klapars, A.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 7421.
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18. Kwong, F. Y.; Klapars, A.; Buchwald, S. L. Org. Lett. 2002, 4, 581.
19. Aqueous hydroxide as a base for palladium-catalyzed amination has been reported; however, a phase transfer catalyst and toluene cosolvent were required: (a) Kuwano, R.; Utsunomiya, M.; Hartwig, J. F. J. Org. Chem. 2002, 67, 6479. For the use of solid NaOH in dioxane, see: (b) Grasa, G. A.; Viciu, M. S.; Huang, J.; Nolan, S. P. J. Org. Chem. 2001, 66, 7729.
20. Aqueous hydroxide as a base for palladium-catalyzed amination has been reported; however, a phase transfer catalyst and toluene cosolvent were required: (a) Kuwano, R.; Utsunomiya, M.; Hartwig, J. F. J. Org. Chem. 2002, 67, 6479. For the use of solid NaOH in dioxane, see: (b) Grasa, G. A.; Viciu, M. S.; Huang, J.; Nolan, S. P. J. Org. Chem. 2001, 66, 7729.
21. - could be used instead of 1 with comparable results. (a) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (b) Netherton, M. R.; Fu, G. C. Org. Lett. 2001, 3, 4295.
22. - could be used instead of 1 with comparable results. (a) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617. (b) Netherton, M. R.; Fu, G. C. Org. Lett. 2001, 3, 4295.
23. 3/1 is more convenient and therefore recommended in the majority of cases. For studies on palladacycles of this type, see: Bedford, R. B.; Cazin, C. S. J.; Coles, S. J.; Gelbrich, T.; Horton, P. N.; Hursthouse, M. B.; Light, M. E. Organometallics 2003, 22, 987.