A remarkable anion effect on the enantioselectivity of the Pd-catalyzed allylic amination using ferrocenyl ligands

Tetrahedron Asymmetry

Volumn 8, Issue 1, 1997, Pages 155-159

  Burckhardt, Urs ^a   Baumann, Markus ^a   Togni, Antonio ^a  

^a ETH ZURICH   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

BENZYLAMINE DERIVATIVE;

AMINATION; ARTICLE; CATALYSIS; DRUG SYNTHESIS; ENANTIOMER; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PRIORITY JOURNAL; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0031016772     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(96)00486-7     Document Type: Article

References (22)

1. For a recent review on catalytic allylic substitution, see: Trost, B.M.; Van Vranken, D.L. Chem. Rev. 1996, 96, 395, and refs cited therein.
2. See, e.g.: (a) Hayashi, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.; Miura, H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301.
3. (b) Bovens, M.; Togni, A.; Venanzi, L.M. J. Organomet. Chem. 1993, 451, C28.
4. (c) Trost, B.M.; Organ, M.G.; O'Doherty, G.A. J. Am. Chem. Soc. 1995, 77, 9662.
5. (d) Trost, B.M.; Bunt, R.C. J. Am. Chem. Soc. 1996, 118, 235.
6. - on p-allyl rotation in stoichiometric systems, see: (e) Hansson, S.; Norrby, P.-O.; Sjögren, M.P.T.; Åkermark, B.; Cucciolito, M.E.; Giordano, F.; Vitagliano, A. Organometallics 1993, 12, 4940.
7. (f) Gogoll, A.; Örnebro, J.; Grennberg, H.; Bäckvall, J.E. J. Am. Chem. Soc. 1994, 116, 3631.
8. (g) Andersson, P.G.; Harden, A.; Tanner, D.; Norrby, P.-O. Chem. Eur. J. 1995, 1, 12. For a general reference, see also: Loupy, A.; Tchoubar, B. Salt Effects in Organic and Organometallic Chemistry, VCH: Weinheim (Germany), 1992.
9. (g) Andersson, P.G.; Harden, A.; Tanner, D.; Norrby, P.-O. Chem. Eur. J. 1995, 1, 12. For a general reference, see also: Loupy, A.; Tchoubar, B. Salt Effects in Organic and Organometallic Chemistry, VCH: Weinheim (Germany), 1992.
10. (a) Catalysis: Togni, A.; Burckhardt, U.; Gramlich, V.; Pregosin, P.S.; Salzmann, R. J. Am. Chem. Soc. 1996, 118, 1031.
11. (b) DFT calculations: Togni, A.; Blöchl, P.E. Organometallics, 1996, 15, 4121.
12. Burckhardt, U.; Hintermann, L.; Schnyder, A.; Togni, A. Organometallics 1995, 14, 5415.
13. Burckhardt, U.; Gramlich, V.; Hofmann, P.; Nesper, R.; Pregosin, P.S.; Salzmann, R.; Togni, A. Organometallics 1996, 15, 3496.
14. The ee of the substrate was periodically monitored. Samples of the reaction solution were quenched on silica and analyzed by HPLC (ref. 3a).
15. See, e.g.: (a) Auburn, P.R.; Mackenzie, P.B.; Bosnich, B. J. Am. Chem. Soc. 1985, 107, 2033.
16. (b) Mackenzie, P.B.; Whelan, J.; Bosnich, B. J. Am. Chem. Soc. 1985, 107, 2046.
17. For a general treatment of the Curtin-Hammett principle, see: (c) Seeman, J.I. Chem. Rev. 1983, 83, 83.
18. Decomposition might proceed via fluorination of the phosphorus atom with concomitant reduction of Pd, as it has been reported for a Pd(II)-PPPP system: Mason, M.R.; Verkade, J.G. Organometallics 1992, 11, 2212.
19. The catalytic performance of 5a and 5b (conversion, ee) is identical to that of the corresponding fluoride complexes generated in situ. Experimental details for the preparation of 5a is given as Supporting Information.
20. a) Hayashi, T.; Kawatsura, M.; Iwamura, Y.; Uozumi, Y. J. Chem. Soc. Chem. Commun. 1996, 1767.
21. b) Bäckvall, J.-E.; Nordberg, R.E.; Wilhelm, D. J. Am. Chem. Soc. 1985, 107, 6892.
22. Estimated turnover rates: in situ catalyst (ligand 3a), 4.5 min; same catalyst +2 equiv./Pd of fluoride, 15 min; and +10 equiv./Pd of fluoride, 100 min.