Palladium-catalyzed synthesis of N-aryl pyrrolidines from γ-(N-arylamino) alkenes: Evidence for chemoselective alkene insertion into Pd-N bonds

Angewandte Chemie - International Edition

Volumn 43, Issue 27, 2004, Pages 3605-3608

  Ney, Joshua E ^a   Wolfe, John P ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

Alkene insertion; Aryl halides; Diastereoselectivity; Nitrogen heterocycles; Palladium

Indexed keywords

BUTANE; CATALYSIS; CHEMICAL BONDS; DERIVATIVES; PALLADIUM; REACTION KINETICS;

PYRROLIDINES; STEREOSELECTIVE SYNTHESIS;

OLEFINS;

ALKENE DERIVATIVE; NITROGEN; PALLADIUM; PYRROLIDINE DERIVATIVE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMICAL BOND; CHEMICAL MODIFICATION; CHEMICAL REACTION KINETICS; COMPLEX FORMATION; STEREOCHEMISTRY;

EID: 4544265647     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200460060     Document Type: Article

References (30)

1. 2) intermediates, see: a) A. R. Muci, S. L. Buchwald, Top. Curr. Chem. 2002, 291, 131-209;
2. b) J. F. Hartwig, Pure Appl. Chem. 1999, 71, 1417-1423.
3. a) J. M. Boncella, L. A. Villanueva, J. Organomet. Chem. 1994, 465, 297-304;
4. b) L. A. Villanueva, K. A. Abboud, J. M. Boncella, Organometallics 1992, 11, 2963-2965.
5. For related studies on the synthesis of tetrahydrofurans, see: J. P. Wolfe, M. A. Rossi, J. Am. Chem. Soc. 2004, 126, 1620-1621.
6. a) D. O'Hagan, Nat. Prod. Rep. 2000, 17, 435-446;
7. b) J. R. Lewis, Nat. Prod. Rep. 2001, 18, 95-128.
8. a) A. Mitchinson, A. Nadin, J. Chem. Soc. Perkin Trans. 1 2000, 2862-2892;
9. b) M. Pichon, B. Figadere, Tetrahedron: Asymmetry 1996, 7, 927-964.
10. For pyrrolidine syntheses that involve intramolecular C-N bond formation and intermolecular C-C bond formation, see: a) Y. Tamaru, M. Kimura, Synlett 1997, 749-757;
11. b) Y. Tamaru, M. Hojo, Z.-i. Yoshida, J. Org. Chem. 1988, 53, 5731-5741;
12. c) H. Yorimitsu, K. Wakabayashi, H. Shinokubo, K. Oshima, Bull. Chem. Soc. Jpn. 2001, 74, 1963-1970;
13. d) R. C. Larock, H. Yang, S. M. Weinreb, R. J. Herr, J. Org. Chem. 1994, 59, 4172-4178.
14. 2)] complex are occasionally observed; see reference [1].
15. G. Fournet, G. Balme, J. Gore, Tetrahedron 1990, 46, 7763-7774.
16. 1H NMR NOE experiments and/or by analogy with related compounds of known configuration.
17. The reaction of 2-bromonaphthalene with N-(4-methoxyphenyl)-3- pentenylamine under the standard reaction conditions afforded only the product of N-arylation; no cyclized products were observed. This result suggests that the regioisomeric products are not formed through initial isomerization of the alkene substrate followed by 5-endocyclization.
18. 1H NMR spectroscopic analysis of the reaction mixture showed that the products 5, 6, 7, and 8 were formed in a ratio of 6:7:2:1. The use of dppe as a ligand led to a 2:1:2:4 ratio of 5/6/7/8, and the use of dppb as a ligand afforded a 2:2:2:1 mixture of 5/6/7/8.
19. The ligands dppe and dppb have been shown to decrease the rate of C-C and C-N bond-forming reductive elimination and increase the formation of side products by competing β-hydride elimination; see: a) A. Gillie, J. K. Stille, J. Am. Chem. Soc. 1980, 102, 4933-4941;
20. b) M. S. Driver, J. F. Hartwig, J. Am. Chem. Soc. 1997, 119, 8232-8245;
21. c) J. P. Wolfe, S. L. Buchwald, J. Org. Chem. 2000, 65, 1144-1157.
22. I. P. Beletskaya, A. V. Cheprakov, Chem. Rev. 2000, 100, 3009-3066.
23. D. Milstein, J. K. Stille, J. Am. Chem. Soc. 1979, 101, 4981-4991.
24. H. Qian, R. A. Widenhoefer, J. Am. Chem. Soc. 2003, 125, 2056-2057.
25. a) J. Helaja, R. Göttlich, Chem. Commun. 2002, 720-721;
26. b) H. Tsutsui, K. Narasaka, Chem. Lett. 1999, 45-46
27. 2] with ethylene or acrylonitrile led to reductive elimination of aniline rather than alkene insertion: A. L. Seligson, R. L. Cowan, W. C. Trogler, Inorg. Chem. 1991, 30, 3371-3381.
28. For examples of insertion reactions of activated alkenes into platinum-nitrogen bonds, see: a) R. L. Cowan, W. C. Trogler, Organometallics 1987, 6, 2451-2453;
29. b) R. L. Cowan, W. C. Trogler, J. Am. Chem. Soc. 1989, 111, 4750-4761.
30. For an example of a catalytic reaction that proceeds through the insertion of norbornene into an iridium-nitrogen bond, see: A. L. Casalnuovo, J. C. Calabrese, D. Milstein, J. Am. Chem. Soc. 1988, 110, 6738-6744.