Industrial-scale palladium-catalyzed coupling of aryl halides and amines - A personal account

Advanced Synthesis and Catalysis

Volumn 348, Issue 1-2, 2006, Pages 23-39

  Buchwald, Stephen L ^a   Mauger, Christelle ^b,e   Mignani, Gerard ^b   Scholz, Ulrich ^c,d  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

^b Rhodia Europe   (France)

^c LANXESS DEUTSCHLAND GMBH   (Germany)

^d BOEHRINGER INGELHEIM PHARMA GMBH AND CO KG   (Germany)

^e RECKITT BENCKISER   (United Kingdom)

Author keywords

Amination; Anilines; C N cross coupling; Homogeneous catalysis; Palladium; Phosphane ligands

Indexed keywords

EID: 31544469241     PISSN: 16154150     EISSN: None     Source Type: Journal    
DOI: 10.1002/adsc.200505158     Document Type: Review

References (57)

1. For a recent review see, for example: V. Farina, Adv. Synth. Catal 2004, 346, 1553-1582.
2. a) T. Kanbara, A. Honma, K. Hasegawa, Chem. Lett. 1996, 1135;
3. b) F. E. Goodson, J. F. Hartwig, Macromolecules 1998, 31, 1700;
4. c) J. Louie, J. F. Hartwig, J. Am. Chem. Soc. 1997, 119, 11695;
5. d) J. Louie, J. F. Hartwig, Macromolecules 1998, 31, 6737;
6. e) R. A. Singer, J. P. Sadighi, S. L. Buchwald, J. Am. Chem. Soc. 1998, 120, 213.
7. a) L. Jiang, S. L. Buchwald, in: Metal-Catalyzed Cross-Coupling Reactions, (Eds.: A. de Meijere, F. Diederich), ISBN 3-527-30518-1, Wiley-VCH, Weinheim, 1998;
8. b) B. Schlummer, U. Scholz, Adv. Synth. Catal. 2004, 346, 1599-1626.
9. a) B. Robinson, The Fischer Indole Synthesis, John Wiley and Sons, Chichester, 1982;
10. b) R. Milcent, Chimie Organique Hétérocyclique, EDP Science, 2002;
11. c) J. Joulie, K. Mills, Heterocyclic Chemistry, Blackwell Publishing, Oxford, 2000;
12. d) I. Gut, J. Wirz, Angew. Chem. Int. Ed. Engl. 1994, 33, 1153;
13. e) R. Sundberg, Indoles, Academic Press, London, 1996.
14. C. Mauger, G. Mignani, Org. Proc. Devel. 2004, 8, 1065.
15. 7, proved to be ineffective.
16. Trifluoromethylphenyl hydrazines are important compounds for the preparation of azaheterocycle intermediates in pharmaceutical and agrochemical domains, for examples, see a) WO 2003076409 (Syngenta Participations AG, Switzerland);
17. b) WO 2003068223 (Bayer Corporation, USA);
18. c) FR 2815346 (Les Laboratoires Servier, France);
19. d) WO 2001089457 (SmithKline Beecham Corporation, USA; Glaxo Group Limited);
20. e) WO 2000069849 (Ortho-McNeil Pharmaceutical, Inc., USA);
21. f) Y. Nalavde, V. Joshi, Ind. J. Chem. Sect. B 2000, 39, 634-637;
22. g) EP 1044970 (Adir et Compagnie, France).
23. 3 (70%). No reaction occurred using A as the ligand.
24. Description of Raman spectrometer: in situ Raman Rxn1 Analyzer from Kaiser Optical Systems Inc., immersion probe with TE-cooled CCD detector technology using laser 785 nm.
25. Quantitative palladium analysis was performed by FX analysis.
26. The highest temperature reached in this exotherm was 192°C.
27. The calorimetric energy displayed during the reaction was measured in a RC1 Mettler calorimeter to be 62.4 kJ/mol of starting arylhydrazone. This heat corresponds to an adiabatic temperature rise of +13.5°C, therefore due to the long reaction time of about 20 h the reaction can be regarded as safe.
28. CASIS Search 01/2004.
29. 1H-NMR.
30. a) F. Ullmann, Ber. dtsch. Chem. Ges. 1901, 34, 2174;
31. b) F. Ullmann, Ber. dtsch chem. Ges. 1903, 36, 2382-2384;
32. c) F. Ullmann, P. Sponagel, Ber. dtsch. chem. Ges. 1905, 36, 2211-2212;
33. d) I. Goldberg, Ber. dtsch. chem. Ges. 1906, 39, 1691-1692;
34. e) S. V. Ley, A. W. Thomas, Angew. Chem. 2003, 115, 5558-5607;
35. Angew. Chem. Int. Ed. 2003, 42, 5400-5449;
36. f) K. Kunz, U. Scholz, D. Ganzer, Synlett 2003, 2428-2439.
37. a) M. K. Stern, J. K Bashkin, WO 9300324;
38. b) R. D. Triplett, R. K. Rains, WO 2003010126;
39. c) S. M. S. Chauhan, R. Singh, Synth. Commun. 2003, 33, 2899-2906.
40. 3.
41. Determined by ICP-MS.
42. German Patent DE 19942394.
43. 75% of the original charcoal precipitated of the Pd/C and could be isolated by filtration. The remaining 10% of palladium could be recovered by addition of CECA 4S activated charcoal and 1 h stirring at 50°C.
44. 2,2-Bis-(4-hydroxybiphenyl)-propane.
45. Lanxess, German Patent DE 10235834.
46. Mitsui, Japanese Patent JP61218560, JP 05003867.
47. a) S. Kaye, J. M. Fox, F. A. Hicks, S. L. Buchwald, Adv. Synth. Catal. 2001, 344, 789;
48. b) X. Huang, K. W. Anderson, D. Zim, L. Jiang, A. Klapars, S. L. Buchwald, J. Am. Chem. Soc. 2003, 125, 6653.
49. Due to the fact that 2,6-dimethoxybromobenzene is not available as a starting material, a separate route for the synthesis of ligand was developed: T. E. Barder, S. D. Walker, J. R. Martinelli, S. L. Buchwald, J. Am. Chem. Soc. 2005, 127, 4685-4696.
50. THF was provided by SDS and contained 0.1% of water.
51. 31P NMR.
52. 31P NMR was > 98%.
53. 31P NMR was 98%, a second crop yielded an additional 10% yield of A.
54. The calorimetric and thermodynamic studies were performed in a 2-liter RC1 Mettler calorimeter.
55. Similar results were obtained for the synthesis of ligand C.
56. F. Rampf, H. C.Militzer, (Lanxess), European Patent EP 1354886, 2003.
57. Determined by calibrated HPLC.