Chiral diketimines as ligands in Pd-catalyzed reactions: Prediction of catalyst activity by the AMS model [24]

Journal of the American Chemical Society

Volumn 122, Issue 5, 2000, Pages 996-997

  Reetz, Manfred T ^a   Haderlein, Gerd ^a   Angermund, Klaus ^a  

^a MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

IMINE;

CATALYSIS; CATALYST; CHEMICAL BOND; CHEMICAL STRUCTURE; LETTER; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0034624411     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9930566     Document Type: Letter

References (28)

1. (a) Clark, J. S.; Fretwell, M.; Whitlock, G. A.; Burns, C. J.; Fox, D. N. A. Tetrahedron Lett. 1998, 39, 97-100.
2. (b) Suga, H.; Fudo, T.; Ibata, T. Synlett 1998, 933-935.
3. (c) Krasik, P.; Alper, H. Tetrahedron 1994, 50, 4347-4354.
4. (d) Evans, D. A.; Lectka, T.; Miller, S. J. Tetrahedron Lett. 1993, 34, 7027-7030.
5. (e) Li, Z.; Conser, K. R.; Jacobsen, E. M. J. Am. Chem. Soc. 1993, 115, 5326-5327.
6. Kuhn, R.; Goldfinger, P. Justus Liebigs Ann. Chem. 1929, 470, 183-200.
7. (a) Helmchen, G. J. Organomet. Chem. 1999, 576, 203-214.
8. (b) Trost, B. M.; van Vranken, D. L. Chem. Rev. (Washington, DC) 1996, 96, 395-422.
9. Angermund, K.; Baumann, W.; Dinjus, E.; Fornika, R.; Görls, H.; Kessler, M.; Krüger, C.; Leitner, W.; Lutz, F. Chem.-Eur. J. 1997, 3, 755-764.
10. Sybyl, version 6.5; Tripos Assoc. Inc.: St. Louis, MO
11. Connolly, M. L. Science 1983, 221, 709-713.
12. (a) Drent, E.; Budzelaar, P. H. M. Chem. Rev. (Washington, DC) 1996, 96, 663-681.
13. (b) Drent, E.: van Broekhoven, J. A. M.; Budzelaar, P. H. M. Recl. Trav. Chim. Pays-Bas 1996, 115, 263-270.
14. (c) Sen, A. Acc. Chem. Res. 1993, 26, 303-310.
15. (d) Drent, E.; van Broekhoven, J. A. M.; Doyle, M. J. J. Organomet. Chem. 1991, 417, 235-251.
16. (e) Drent, E. Pure Appl. Chem. 1990, 62, 661-669.
17. (f) Sen, A. Adv. Polym. Sci. 1986, 73/74, 125-144.
18. (g) Sen, A. CHEMTECH 1986, 48-51.
19. Nozaki, K.; Sato, N.; Tonomura, Y.; Yasutomi, M.; Takaya, H.; Hiyama, T.; Matsubara, T.; Koga, N. J. Am. Chem. Soc. 1997, 119, 12779-12795.
20. Brookhart, M.; Wagner, M. I.; Balavoine, G. G. A.; Haddou, H. A. J. Am. Chem. Soc. 1994, 116, 3641-3642.
21. Sperrle, M.; Aeby, A.; Consiglio, G.; Pfaltz, A. Helv. Chim. Acta 1996, 79, 1387-1392.
22. Keim, W.; Maas, H. J. Organomet. Chem. 1996, 514, 271-276.
23. (a) Jiang, Z.; Sen, A. J. Am. Chem. Soc. 1995, 117, 4455-4467.
24. (b) Sperrle, M.; Consiglio, G. J. Am. Chem. Soc. 1995, 117, 12130-12136.
25. (c) Bronco, S.; Consiglio, G.; Hutter, R.; Batistini, A.; Suter, U. W. Macromolecules 1994, 27, 4436-4440.
26. (d) Jiang, Z.; Adams, S. E.; Sen, A. Macromolecules 1994, 27, 2694-2700.
27. (e) Barsacchi, M.; Batistini, A.; Consiglio, G.; Suter, U. W. Macromolecules 1992, 25, 3604-3606.
28. In spite of the crudeness of the AMS model, it is in line with the experimental results. Nevertheless, knowledge of transition states and rate-determining steps will in general be required to make predictions about catalyst activity. For example, in the copolymerization the insertion of the olefin in the Pd-acyl bond, which is believed to be the rate-determining step, requires an open and accessible site for the olefin. Extremely open catalysts species, however, may form very stable intermediates, such that the subsequent CO insertion could then become the rate-limiting step for those catalysts, making comparisons difficult. The AMS concept is a computationally fast and intuitive way to distinguish between active and less active catalysts in a homologous series, provided that they react in a similar way. It can be applied even to molecular systems in which the size of the species considered prohibits the use of sophisticated methods. Because of the modeling type of approach, the results obtained by the AMS concept should be applied with the appropriate care.