Ligand-dependent mechanistic dichotomy in iron-catalyzed allylic substitutions: σ-allyl versus π-allyl mechanism

Angewandte Chemie - International Edition

Volumn 47, Issue 1, 2008, Pages 198-201

  Plietker, Bernd ^a   Dieskau, André ^a   Möws, Katrin ^a   Jatsch, Anja ^a  

^a UNIVERSITY OF STUTTGART   (Germany)

Author keywords

Allylic compounds; Iron; Nucleophilic substitution; Regioselectivity; Stereoselectivity

Indexed keywords

ALKYLATION; LIGANDS; REGIOSELECTIVITY; STEREOSELECTIVITY; SUBSTITUTION REACTIONS;

ALLYLIC COMPOUNDS; MECHANISTIC DICHOTOMY; NUCLEOPHILIC SUBSTITUTION;

IRON;

EID: 37549040192     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200703874     Document Type: Article

References (41)

1. U. Kazmaier, M. Pohlmann in Metal-Catalyzed Cross-Coupling Reactions, Vol. 2, 2nd ed. (Ed.: A. De Meijere, F. Diederich), Wiley-VCH, Weinheim, 2004, p. 531.
2. B. M. Trost, M. L. Crawley, Chem. Rev. 2003, 103, 2921.
3. a) B. M. Trost, K. Dogra, I. Hachiya, T. Emura, D. L. Hughes, S. W. Krska, R. A. Reamer, M. Palucki, N. Yasuda, P. J. Reider, Angew. Chem. 2002, 114, 2009;
4. Angew. Chem. Int. Ed. 2002, 41, 1929;
5. b) F. Glorius, A. Pfaltz, Org. Lett. 1999, 1, 141.
6. For a review on iridium-catalyzed asymmetric allylic substitutions, see: G. Helmchen, A. Dahnz, P. Dübon, M. Schelwies, R. Weihofen, Chem. Commun. 2007, 675.
7. a) Y. Morisaki, T. Kondo, T.-A. Misudo, Organometallics 1999, 18, 4742;
8. b) B. M. Trost, P. Fraisse, Z. Ball Angew. Chem. 2002, 114, 1101;
9. Angew. Chem. Int. Ed. 2002, 41, 1059;
10. Angew. Chem. Int. Ed. 2002, 41, 1059;
11. c) M. D. Mbaye, B. Demerseman, J.-L. Renaud, L. Toupet, C. Bruneau, Angew. Chem. 2003, 115, 5220;
12. Angew. Chem. Int. Ed. 2003, 42, 5066;
13. d) R. Hermatschweiler, I. Fernandez, F. Breher, P. S. Pregosin, L. F. Veiros, M. J. Calhorda, Angew. Chem. 2005, 117, 4471;
14. Angew. Chem. Int. Ed. 2005, 44, 4397.
15. a) K.-G. Chung, Y. Miyake, S. Uemura, J. Chem. Soc. Perkin Trans. 1 2000, 15;
16. b) M. T. Didiuk, J. P. Morken, A. H. Hoveyda, J. Am. Chem. Soc. 1995, 117, 7273.
17. D. K. Leahy, P. A. Evans, in Modern Rhodium-Catalyzed Organic Reactions (Ed.: P. A. Evans), Wiley-VCH, Weinheim, 2005, pp. 191.
18. a) B. Plietker, Angew. Chem. 2006, 118, 1497;
19. Angew. Chem. Int. Ed. 2006, 45, 1469;
20. b) B. Plietker, Angew. Chem. 2006, 118, 6200;
21. Angew. Chem. Int. Ed. 2006, 45, 6053.
22. a) Review on iron catalysis: C. Bolm, J. Legros, J. Le Paih, L. Zani, Chem. Rev. 2004, 104, 6217;
23. b) Review on iron-catalyzed cross coupling: A. Fürstner, R. Martin, Chem. Lett. 2005, 34, 624.
24. a) J.-L. Roustan, M. Abedini, H. H. Baer, Tetrahedron Lett. 1979, 20, 3721;
25. b) J.-L. Roustan, M. Abedini, H. H. Baer, J. Organomet. Chem. 1989, 376, C20.
26. a) Y. Xu, B. Zhou, J. Org. Chem. 1987, 52, 974;
27. b) B. Zhou, Y. Xu, J. Org. Chem. 1988, 53, 4421.
28. Reviews on the stoichiometric use of allyl iron complexes: a) S. V. Ley, R. Liam, G. Meek, Chem. Rev. 1996, 96, 423;
29. b) D. Enders, B. Jandeleit, S. von Berg, Synthesis 1997, 421;
30. c) D. Enders, B. Jandeleit, S. von Berg, G. Raabe, J. Runsink, Organometallics 2001, 20, 4312, and references therein.
31. N-Heterocyclic Carbenes in Transition Metal Cataylsis (Ed.: F. Glorius), Springer, Hamburg, 2007.
32. For the influence of monodentate phosphane ligands see the Supporting Information.
33. Details on the reaction optimization are provided in the Supporting Information.
34. R. B. Bedford, M. Betham, D. W. Bruce, A. A. Danopoulos, R. M. Frost, M. Hird, J. Org. Chem. 2006, 71, 1104.
35. N2′-type mechanism. The subsequent reaction of the allyl iron complex with the nucleophile would then lead to inversion of regioselectivity.
36. a table: http://www.chem. wisc.edu/ areas/reich/pkatable/.
37. a) H. Mayr, B. Kempf, A. R. Ofial, Acc. Chem. Res. 2003, 36, 66;
38. b) Taken from H. Mayr's s-N-E database: http://cicum92.cup. uni-muenchen.de/mayr/reaktionsdatenbank/.
39. The nature of the leaving group had only a minor influence on the regioselectivity (see Supporting Information).
40. See Supporting Information.
41. A similar reaction has only been known in the presence of rhodium catalysts: B. L. Ashfeld, K. A. Miller, S. F. Martin, Org. Lett. 2004, 6, 1321.