Mechanistic analysis of azine N-oxide direct arylation: Evidence for a critical role of acetate in the Pd(OAc)2 precatalyst

Journal of Organic Chemistry

Volumn 75, Issue 23, 2010, Pages 8180-8189

  Sun, Ho Yan ^a   Gorelsky, Serge I ^a   Stuart, David R ^a   Campeau, Louis Charles ^a   Fagnou, Keith ^a  

^a UNIVERSITY OF OTTAWA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ARYLATIONS; C-H BOND; C-H BOND CLEAVAGE; COMPUTATIONAL STUDIES; ELECTRON-DEFICIENT SPECIES; MECHANISTIC ANALYSIS; MECHANISTIC STUDIES; METALATIONS; N-OXIDES; PRECATALYSTS; REACTION MECHANISM; TRANSITION STATE;

AROMATIC COMPOUNDS; CARBOXYLATION; REACTION RATES; SPHERES;

PALLADIUM;

ACETIC ACID; AZINE N OXIDE; BASE; OXIDE; PALLADIUM ACETATE; PALLADIUM OXIDE ACETATE; PYRIDINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; ARYLATION; CARBOXYLATION; CATALYST; CHEMICAL BOND; CHEMICAL REACTION KINETICS; CONCERTED METALATION DEPROTONATION; CROSS COUPLING REACTION; ELECTRON TRANSPORT; HYDROGEN BOND; METALLATION; PROTON TRANSPORT;

EID: 78650299781     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo101821r     Document Type: Article

References (55)

1. For comprehensive reviews on direct arylations, see: Ackermann, L.; Vicente, R.; Kapdi, A. R. Angew. Chem., Int. Ed. 2009, 48, 9792
2. Campeau, L.-C.; Stuart, D. R.; Fagnou, K. Aldrichim. Acta 2007, 40, 35
3. Alberico, D.; Scott, M. E.; Lautens, M. Chem. Rev. 2007, 107, 174
4. Modern Arylation Methods; Ackermann, L., Ed.; Wiley-VCH: Weinheim, German y, 2009.
5. Park, C.-H.; Ryabova, V.; Seregin, I. V.; Sromek, A. W.; Gevorgyan, V. Org. Lett. 2004, 6, 1159
6. Lane, B. S.; Brown, M. A.; Sames, D. J. Am. Chem. Soc. 2005, 127, 8050
7. Chuprakov, S.; Chernyak, N.; Dudnik, A. S.; Gevorgyan, V. Org. Lett. 2007, 9, 2333
8. Lafrance, M.; Rowley, C. N.; Woo, T. K.; Fagnou, K. J. Am. Chem. Soc. 2006, 128, 8754
9. Campeau, L.-C.; Rousseaux, S.; Fagnou, K. J. Am. Chem. Soc. 2005, 127, 18021
10. Campeau, L.-C.; Stuart, D. R.; Leclerc, J.-P.; Bertrand-Laperle, M.; Villemure, E.; Sun, H.-Y.; Lasserre, S.; Guimond, N.; Lecavallier, M.; Fagnou, K. J. Am. Chem. Soc. 2009, 131, 3291
11. Garcia-Cuadrado, D.; Braga, A. A. C.; Maseras, F.; Echavarren, A. M. J. Am. Chem. Soc. 2006, 128, 1066
12. García-Cuadrado, D.; de Mendoza, P.; Braga, A. A. C.; Maseras, F.; Echavarren, A. M. J. Am. Chem. Soc. 2007, 129, 6880
13. Pivsa-Art, S.; Satoh, T.; Kawamura, Y.; Miura, M.; Nomura, B. Bull. Chem. Soc. Jpn. 1998, 71, 467
14. Yanagisawa, S.; Sudo, T.; Noyori, R.; Itami, K. J. Am. Chem. Soc. 2006, 128, 11748
15. McClure, M. S.; Glover, B.; McSorley, E.; Millar, A.; Osterhout, M. H; Roschanger, F. Org. Lett. 2001, 3, 1677
16. Glover, B.; Harvey, K. A.; Liu, B.; Sharp, M. J.; Tymoschenko, M. F. Org. Lett. 2003, 5, 301
17. Li, W.; Nelson, D. P.; Jensen, M. S.; Hoerrner, R. S.; Javadi, G. J.; Cai., D.; Larsen, R. D. Org. Lett. 2003, 5, 4835
18. Wang, J.-X.; McCubbin, J. A.; Jin, M.; Laufer, R. S.; Mao, Y.; Crew, A. P.; Mulvihill, M. J.; Snieckus, V. Org. Lett. 2008, 10, 2923 and references cited therein.
19. Okazawa, T.; Satoh, T.; Miura, M.; Nomura, M. J. Am. Chem. Soc. 2002, 124, 5286
20. Campo, M. A.; Huang, Q.; Yao, T.; Tian, Q.; Larock, R. C. J. Am. Chem. Soc. 2003, 125, 11506
21. Capito, E.; Brown, J. M.; Ricci, A. Chem. Commun. 2005, 1854
22. Gorelsky, S. I.; Lapointe, D.; Fagnou, K. J. Am. Chem. Soc. 2008, 130, 10848
23. Zhao, X.; Yeaung, C. S.; Dong, V. M. J. Am. Chem. Soc. 2010, 132, 5837
24. Davies, D. L.; Donald, S. M. A.; Macgregor, S. A. J. Am. Chem. Soc. 2005, 127, 13754
25. Biswas, B.; Sugimoto, M.; Sakaki, S. Organometallics 2000, 19, 3895
26. 1H NMR.
27. For results from a one-pot KIE experiment, please see ref 4a.
28. Fairlie, D. P.; Bosnich, B. Organometallics 1988, 7, 946
29. Van Strijdonck, G. F. P.; Boele, M. D. K.; Kamer, P. C. J.; de Vries, J. G.; van Leeuwen, P. W. N. M. Eur. J. Inorg. Chem. 1999, 1073
30. Kina, A.; Hiroshi, I.; Hayashi, T. J. Am. Chem. Soc. 2006, 128, 3904
31. Collum, D. B.; McNeil, A. J.; Ramirez, A. Angew. Chem., Int. Ed. 2007, 46, 3002
32. Shen, Z.; Dornan, P. K.; Khan, H. A.; Woo, T. K.; Dong, V. M. J. Am. Chem. Soc. 2009, 131, 1077
33. Stambuli, J. P.; Bühl, M.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 9346
34. Ziegler, T.; Autschbach, J. Chem. Rev. 2005, 105, 2695
35. Hohenburg, P.; Kohn, W. Phys. Rev. B 1964, 136, 864
36. Kohn, W.; Sham, L. J. Phys. Rev. A 1965, 140, 1133
37. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785
38. Schafer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100, 5829
39. Godbout, N.; Salahub, D. R.; Andzelm, J.; Wimmer, E. Can. J. Chem. 1992, 70, 560
40. Foresman, J. B.; Keith, T. A.; Wiberg, K. B.; Snoonian, J.; Frisch, M. J. J. Phys. Chem. 1996, 100, 16098
41. Pascual, S.; de Mendoza, P.; Braga, A. A. C.; Maseras, F.; Echavarren, A. M. Tetrahedron 2008, 64, 6021
42. Lafrance, M.; Fagnou, K. J. Am. Chem. Soc. 2006, 128, 16496
43. Andersson, H.; Almqvist, F.; Olsson, R. Org. Lett. 2007, 9, 1335
44. Taylor, E. C., Jr.; Crovetti, A. J. Organic Syntheses; Wiley: New York, 1963; Collect. Vol. IV, p 654; 1956; Vol. 36, p 53.
45. Paudler, W. W.; Humphrey, S. A. J. Org. Chem. 1970, 35, 3467
46. Kreuger, S. A.; Paudler, W. W. J. Org. Chem. 1972, 37, 4188
47. Schipper, D. J.; El-Salfiti, M.; Whipp, C. J.; Fagnou, K. Tetrahedron 2009, 4977
48. The regioselectivities for 3-fluoro- and 3-phenylpyridine N -oxide have also been reproduced stoichiometrically with 2. See the Supporting Information.
49. While reactions having 10-30 mol % carboxylate have similar rates, it was noticed that when >40 mol % carboxylate is present under the standard conditions, a significant rate decrease is observed.
50. To test this hypothesis, the rate of a reaction using a catalytic amount of KOAc was measured, but was found to be quite slow, likely due to the insolubility of KOAc in the toluene.
51. 2, see the Supporting Information.
52. Barrios-Landeros, F. Oxidative Addition of Haloarenes by Pd(0) Complexes of Bulky Alkyl Phosphines: Synthesis of Intermediates and Mechanistic Studies, Dissertation, Yale University, 2007.
53. 3 (2 equiv), PhMe, 110 °C, 16 h. NMR yield of 62%.
54. Efforts to isolate and characterize the dimeric resting state of the catalyst were unfruitful. However, as both the Pd-Br (1) and Pd-OAc (2) are known to be monomeric, we suspect the involvement of pyridine N -oxide in the dimeric form.
55. It is likely that the inital coordination of pyridine N -oxide occurs via oxygen; for references on O-bound Pd complexes, see: Cho, S. H.; Hwang, S. J.; Chang, S. J. Am. Chem. Soc. 2008, 130, 9254