Ligand-free palladium-catalyzed cyanation of aryl halides

Journal of Organic Chemistry

Volumn 70, Issue 4, 2005, Pages 1508-1510

  Weissman, Steven A ^a   Zewge, Daniel ^a   Chen, Cheng ^a  

^a MERCK RESEARCH LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; COMPLEXATION; CYANIDES; IRON COMPOUNDS; PALLADIUM;

ARYL HALIDES; CYANATION; NONTOXIC CYANIDES;

REACTION KINETICS;

CYANIDE; HALIDE; NITRILE; PALLADIUM; POTASSIUM; SODIUM;

ARTICLE; CHEMICAL REACTION KINETICS; COMBINATORIAL CHEMISTRY; CYANATION; ELIMINATION REACTION; LIGAND BINDING; METAL BINDING; METHODOLOGY; PRODUCT RECOVERY; REACTION ANALYSIS; REACTION OPTIMIZATION;

EID: 13844320088     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0481250     Document Type: Article

References (32)

1. For example, The Merck Index (13th ed.; O'Neil, M. J., Ed.; Merck: 2001) lists 22 compounds that incorporate this functionality: Monograph nos. 926, 1098, 1204, 1426, 1446, 1477, 2185, 2283, 2299, 2342, 2712, 2720, 3068, 3958, 5469, 5481, 5576, 6690, 7242, 9615.
2. Chemistry of the Cyano Group; Rappoport, Z., Ed.; John Wiley & Sons: London 1970.
3. (a) For a review, see: Mowry, D. T. Chem. Rev. 1948, 42, 189-283.
4. (b) For improved conditions, see: Friedman, L.; Shechter, H. J. Org. Chem. 1961, 26, 2522-2524.
5. Takagi, K.; Okamoto, T.; Sakakibara, Y.; Oka, S. Chem. Lett. 1973, 5, 471-4.
6. Takagi, K.; Okamoto, T.; Yasumasa, S.; Ohno, A.; Oka, S.; Hayama, N. Bull. Chem. Soc. Jpn. 1975, 48, 3298-3301.
7. For reviews, see: (a) Sundermeier, M.; Zapf, A.; Beller, M. Eur. J. Inorg. Chem. 2003, 3513-3526. (b) Takagi, K. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E., Ed.; J. Wiley & Sons: Hoboken, NJ, 2002; Vol. 1, pp 657-672.
8. For reviews, see: (a) Sundermeier, M.; Zapf, A.; Beller, M. Eur. J. Inorg. Chem. 2003, 3513-3526. (b) Takagi, K. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E., Ed.; J. Wiley & Sons: Hoboken, NJ, 2002; Vol. 1, pp 657-672.
9. Chidambaram, R. Tetrahedron Lett. 2004, 1441-1444.
10. Sundermeier, M.; Zapf, A.; Mutyala, S.; Baumann, W.; Sans, J.; Weiss, S.; Beller, M. Chem. Eur. J. 2003, 9, 1828-1836.
11. Okano, T.; Iwahara, M.; Kiji, J. Synlett 1998, 243-244.
12. Yang, C.; Williams, J. M. Org. Lett. 2004, 6, 2837-2840.
13. TMS-CN: Sundermeier, M.; Mutyala, S.; Zapf, A.; Spannenberg, A.; Beller, M. J. Organomet. Chem. 2003, 684, 50-55. Acetone cyanohydrin: Sundermeier, M.; Zapf, A.; Beller, M. Angew. Chem., Int. Ed. 2003, 42, 1661-1664.
14. TMS-CN: Sundermeier, M.; Mutyala, S.; Zapf, A.; Spannenberg, A.; Beller, M. J. Organomet. Chem. 2003, 684, 50-55. Acetone cyanohydrin: Sundermeier, M.; Zapf, A.; Beller, M. Angew. Chem., Int. Ed. 2003, 42, 1661-1664.
15. Use of zinc cyanide in this capacity was introduced by: Tschaen, D. M.; Desmond, R.; King, A. O.; Fortin, M. C.; Pipik, B.; King, S.; Verhoeven, T. R. Synth. Commun. 1994, 24, 887-890.
16. Schareina, T.; Zapf, A.; Beller, M. Chem. Commun. 2004, 12, 1388-1389. We observed no need to dehydrate (3 equiv of water present) this reagent as was described by the authors in this reference. The reagent particle size is critical, as material obtained from Alfa/ Aesar performed well (mean particle size 312 μm; 90% <509 μm), while material from Acros (mean particle size 464 μm; 90% <822 μm) showed only 5% conversion to benzonitrile after 10 h at 120°C. The latter material performed typically (99% conversion/1 h) after pulverization to values of 184 and 374 μm, respectively.
17. First use of potassium ferrocyanide in this capacity (uncatalyzed reaction): Merz, V.; Weith, W. Ber. 1877, 10, 746-765.
18. 6] (aka yellow prussiate of potash) is used as a food additive in table salt to prevent "caking" and in wine production to precipitate metals. The lower toxicity is attributed to the tight bond between the iron center and the CN groups.
19. (a) de Vries, A. H. M.; Mulders, J. M. C. A.; Mommers, J. H. M.; Henderickx, H. J. W.; de Vries, J. G. Org. Lett. 2003, 5, 3285-3288.
20. (b) Reetz, M. T.; de Vries, J. G. Chem. Commun. 2004, 1559-1563.
21. de Vries, J. G.; de Vries, A. H. M. Eur. J. Org. Chem. 2003, 799-811.
22. Urgaonkar, S.; Verkade, J. G. J. Org. Chem. 2004, 69, 5752-5755.
23. Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066.
24. Term "homeopathic quantity" refers to low loadings of ligand-free palladium (generally 0.1 mol % or lower). See ref 18.
25. Li, J.-H.; Liu, W.-J. Org. Lett. 2004, 6, 2809-2811. Reetz, M. T.; Westermann, E.; Lohmer, R.; Lohmer, G. Tetrahedron Lett. 1998, 39, 8449-8452.
26. Li, J.-H.; Liu, W.-J. Org. Lett. 2004, 6, 2809-2811. Reetz, M. T.; Westermann, E.; Lohmer, R.; Lohmer, G. Tetrahedron Lett. 1998, 39, 8449-8452.
27. Marcantonio, K. M.; Frey, L. F.; Liu, Y.; Chen, Y.; Strine, J.; Phenix, B.; Wallace, D.; Chen, C. Org. Lett. 2004, 6, 3723-3725.
28. 2O), also known as yellow prussiate of soda, also can be used as the cyanide source with equal performance.
29. 3 in DMAC (0.6-0.7 M) at 120°C.
30. Increasing the temperature to 130°C had no effect on further conversion.
31. 2 to Pd(0) in propylene carbonate at 100°C has been observed and might be a factor in this system as well. See: Reetz, M.; Lohmer, G. Chem. Commun. 1996, 1921-1922.
32. 3 also provides a nearly equivalent outcome for bromoketone 1.