Intramolecular alkene aminopalladation reactions of (dppf)Pd(Ar)[N(Ar 1)(CH2)3CH-CH2] complexes. Insertion of unactivated alkenes into Pd-N bonds

Journal of the American Chemical Society

Volumn 132, Issue 18, 2010, Pages 6276-6277

  Neukom, Joshua D ^a   Perch, Nicholas S ^a   Wolfe, John P ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BENZYL-PYRROLIDINE; DEUTERIUM LABELING; MIGRATORY INSERTION; ORDER OF MAGNITUDE; REDUCTIVE ELIMINATION;

DEUTERIUM; OLEFINS; PALLADIUM; REACTION INTERMEDIATES; STEREOCHEMISTRY; SYNTHESIS (CHEMICAL);

PALLADIUM COMPOUNDS;

ALKENE; NITROGEN; PALLADIUM; ORGANOMETALLIC COMPOUND;

AMINOPALLADATION; ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; COMPLEX FORMATION; STEREOCHEMISTRY; SYNTHESIS; CATALYSIS; CHEMISTRY; KINETICS;

ALKENES; CATALYSIS; KINETICS; NITROGEN; ORGANOMETALLIC COMPOUNDS; PALLADIUM;

EID: 77953069007     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja9102259     Document Type: Article

References (41)

1. Seligson, A. L., Cowan, R. L., and Trogler, W. C. Inorg. Chem. 1991, 30, 3371
2. 2Pd(Ph)(NHPh) complex has been reported. See
3. Villanueva, L. A., Abboud, K. A., and Boncella, J. M. Organometallics 1992, 11, 2963
4. Bäckvall, J. E. Acc. Chem. Res. 1983, 16, 335
5. Åkermark, B., Bäckvall, J. E., Siirala-Hansen, K., Sj-berg, K., and Zetterberg, K. Tetrahedron Lett. 1974, 15, 1363
6. Ney, J. E. and Wolfe, J. P. J. Am. Chem. Soc. 2005, 127, 8644
7. Bertrand, M. B., Neukom, J. D., and Wolfe, J. P. J. Org. Chem. 2008, 73, 8851
8. Mu-iz, K., H-velmann, C. H., and Streuff, J. J. Am. Chem. Soc. 2008, 130, 763
9. Du, H., Zhao, B., and Shi, Y. J. Am. Chem. Soc. 2007, 129, 762
10. Liu, G. and Stahl, S. S. J. Am. Chem. Soc. 2007, 129, 6328
11. Brice, J. L., Harang, J. E., Timokhin, V. I., Anastasi, N. R., and Stahl, S. S. J. Am. Chem. Soc. 2005, 127, 2868
12. Helaja, J. and G-ttlich, R. J. Chem. Soc., Chem. Commun. 2002, 720
13. Liu, G. and Stahl, S. S. J. Am. Chem. Soc. 2006, 128, 7179
14. Tsutsui, H. and Narasaka, K. Chem. Lett. 1999, 45
15. For reviews on metal-catalyzed reactions that involve syn -alkene insertion into Pd-N bonds, see
16. Wolfe, J. P. Synlett 2008, 2913
17. Minatti, A. and Mu-iz, K. Chem. Soc. Rev. 2007, 36, 1142
18. Kotov, V., Scarborough, C. C., and Stahl, S. S. Inorg. Chem. 2007, 46, 1910
19. For rare examples of insertion of alkenes into Rh-N, Pt-N, or Ir-N bonds, see
20. Zhao, P., Krug, C., and Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 12066
21. Cowan, R. L. and Trogler, W. C. Organometallics 1987, 6, 2451
22. Casalnuovo, A. L., Calabrese, J. C., and Milstein, D. J. Am. Chem. Soc. 1988, 110, 6738
23. Hoover, J. M., DiPasquale, A., Mayer, J. M., and Michael, F. E. J. Am. Chem. Soc. 2010, 132, 5043
24. For a related intramolecular insertion of an unactivated alkene into a Rh-O bond, see
25. Zhao, P., Incarvito, C. D., and Hartwig, J. F. J. Am. Chem. Soc. 2006, 128, 9642
26. dppf = 1,1′-bis(diphenylphosphino)ferrocene.
27. Yamashita, M., Cuevas Vicario, J. V., and Hartwig, J. F. J. Am. Chem. Soc. 2003, 125, 16347
28. Widenhoefer, R. A., Zhong, H. A., and Buchwald, S. L. J. Am. Chem. Soc. 1997, 119, 6787
29. 31P NMR (-45 °C): δ 9.3 (br), 24.3 (d, J = 38 Hz).
30. Detectable amounts of intermediate A were observed after 2 min at rt.
31. -1 at 0 °C. See
32. Brown, J. M. and Guiry, P. J. Inorg. Chim. Acta 1994, 220, 249
33. Culkin, D. A. and Hartwig, J. F. Organometallics 2004, 23, 3398
34. See the Supporting Information for a detailed description of the structural assignment of 6a and the stereochemical assignment of 4c.
35. CP: 9 Hz (cis), 97 Hz (trans).
36. 2.
37. 4- p -CN) derivative 3b was employed for these studies as it reacted at a slower rate than 3a, which simplified experimental setup and allowed for rates to be measured over a range of temperatures above rt.
38. Perch, N. S. and Widenhoefer, R. A. J. Am. Chem. Soc. 2004, 126, 6332
39. Rix, F. C. and Brookhart, M. J. Am. Chem. Soc. 1995, 117, 1137
40. Ermer, S. P., Struck, G. E., Bitler, S. P., Richards, R., Bau, R., and Flood, T. C. Organometallics 1993, 12, 2634
41. Moravskiy, A. and Stille, J. K. J. Am. Chem. Soc. 1981, 103, 4182