Rate Enhancement and Enantioselectivity of the Jacobsen - Katsuki Epoxidation: The Significance of the Sixth Coordination Site

Angewandte Chemie - International Edition

Volumn 40, Issue 11, 2001, Pages 2073-2076

  El Bahraoui, Jaouad ^a   Wiest, Olaf ^a   Feichtinger, Derek ^b   Plattner, Dietmar A ^b  

^a UNIVERSITY OF NOTRE DAME   (United States)

^b ETH ZURICH   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001360369     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20010601)40:11<2073::AID-ANIE2073>3.0.CO;2-Y     Document Type: Article

References (30)

1. W. Zhang, J. L. Loebach, S. R. Wilson, E. N. Jacobsen, J. Am. Chem. Soc. 1990, 112, 2801.
2. R. Irie, K. Noda, Y. Ito, N. Matsumoto, T. Katsuki, Tetrahedron Lett. 1990, 31, 7345.
3. For recent overviews, see: a) Y. N. Ito, T. Katsuki, Bull. Chem. Soc. Jpn. 1999, 72, 603; b) E. N. Jacobsen, Acc. Chem. Res. 2000, 33, 421; c) C. T. Dalton, K. M. Ryan, V. M. Wall, C. Bousquet, D. G. Gilheany, Top. Catal. 1998, 5, 75; d) T. Katsuki, Coord. Chem. Rev. 1995, 140, 189.
4. For recent overviews, see: a) Y. N. Ito, T. Katsuki, Bull. Chem. Soc. Jpn. 1999, 72, 603; b) E. N. Jacobsen, Acc. Chem. Res. 2000, 33, 421; c) C. T. Dalton, K. M. Ryan, V. M. Wall, C. Bousquet, D. G. Gilheany, Top. Catal. 1998, 5, 75; d) T. Katsuki, Coord. Chem. Rev. 1995, 140, 189.
5. For recent overviews, see: a) Y. N. Ito, T. Katsuki, Bull. Chem. Soc. Jpn. 1999, 72, 603; b) E. N. Jacobsen, Acc. Chem. Res. 2000, 33, 421; c) C. T. Dalton, K. M. Ryan, V. M. Wall, C. Bousquet, D. G. Gilheany, Top. Catal. 1998, 5, 75; d) T. Katsuki, Coord. Chem. Rev. 1995, 140, 189.
6. For recent overviews, see: a) Y. N. Ito, T. Katsuki, Bull. Chem. Soc. Jpn. 1999, 72, 603; b) E. N. Jacobsen, Acc. Chem. Res. 2000, 33, 421; c) C. T. Dalton, K. M. Ryan, V. M. Wall, C. Bousquet, D. G. Gilheany, Top. Catal. 1998, 5, 75; d) T. Katsuki, Coord. Chem. Rev. 1995, 140, 189.
7. a) E. N. Jacobsen in Catalytic Asymmetric Synthesis (Ed.: I. Ojima), VCH, Weinheim, 1993, chap. 4.2;
8. b) E. N. Jacobsen in Comprehensive Organometallic Chemistry 11, Vol. 12 (Eds.: G. W. Wilkinson, F. G. A. Stone, E. W. Abel. L. S. Hegedus). Pergamon, New York, 1995, chap. 11.1.
9. a) D. Feichtinger, D.A. Plattner, Angew. Chem. 1997, 109, 1796; Angew. Chem. Int. Ed. Engl. 1997, 36, 1718;
10. a) D. Feichtinger, D.A. Plattner, Angew. Chem. 1997, 109, 1796; Angew. Chem. Int. Ed. Engl. 1997, 36, 1718;
11. b) D. A. Plattner, D. Feichtinger, J. El-Bahroui, O. Wiest, Int. J. Mass Spectrom. 2000, 195/ 196, 351;
12. c) D. Feichtinger, D. A. Planner, J. Chem. Soc. Perkin Trans. 2 2000, 1023;
13. d) D. Feichtinger, D. A. Plattner, Chem. Eur. J. 2001, 7, 591.
14. a) M. Palucki, N. S. Finney, P. J. Pospisil, M. L. Güler, T. Isida, E. N. Jacobsen, J. Am. Chem. Soc. 1998, 120, 948;
15. b) P. J. Pospisil, D. H. Carsten, E. N. Jacobsen, Chem. Eur. J. 1996, 2, 974.
16. a) C. Linde, B. Åkermark, P.-O. Norrby, M. Svenson, J. Am. Chem. Soc: 1999, 121, 5083;
17. b) L. Cavallo, H. Jacobsen, Angew. Chem. 2000, 112, 602; Angew. Chem. Int. Ed. 2000. 39. 589;
18. b) L. Cavallo, H. Jacobsen, Angew. Chem. 2000, 112, 602; Angew. Chem. Int. Ed. 2000. 39. 589;
19. c) T. Strassner, K. N. Houk, Org. Lett. 1999, 1, 419.
20. All geometries were fully optimized by using the B3LYP/6-311G * method and the Gaussian 98 suite of programs. All energies reported are relative to the most stable conformation of the triplet state and are not zero-point corrected. All distances are in Ångstrom, all angles are reported in degrees.
21. a) R. Irie, Y. Ito, T. Katsuki, Synlett 1991, 265;
22. b) N. S. Finney, P. J. Pospisil, S. Chang, M. Palucki, R. G. Konsler, K. B. Hansen, E. N. Jacobsen, Angew. Chem. 1997, 109, 1798; Angew. Chem. Int. Ed. Engl. 1997, 36, 1720.
23. b) N. S. Finney, P. J. Pospisil, S. Chang, M. Palucki, R. G. Konsler, K. B. Hansen, E. N. Jacobsen, Angew. Chem. 1997, 109, 1798; Angew. Chem. Int. Ed. Engl. 1997, 36, 1720.
24. It should be pointed out that the role of spin contamination in Kohn-Sham theory is not clear. For a more extensive discussion see: W. Koch. M. C. Holthausen, A Chemist's Guide to Density Functional Theory, Wiley-VCH, Weinheim, 2000.
25. These would also be similar to the "bent" conformation proposed for chromium - salen complexes: K.M. Ryan, C. Bousquet, D.G. Gilheany, Tetrahedron Lett. 1999, 40, 3613.
26. Further evidence for the electronic nature of this effect comes from preliminary B3LYP/3-21G * calculations of the catalyst bearing an axial OCl ligand. As in the case of trimethylamine N-oxide, the ligation of hypochlorite leads to highly nonplanar conformations. Similarly, inspection of the calculated structure of a Cl -ligated Mn-salen model catalyst depicted in ref. [7b] reveals a strong tendency for a nonplanar conformation.
27. K. Miura, T. Katsuki, Synlett 1999, 783.
28. For examples of such calculations, see: a) J. N. Harvey, M. Aschi, H. Schwarz, W. Koch, Theor. Chem. Acc. 1998, 99, 95; b) S. Mitchell, M. Blitz, P, Siegbahn, M. Svensson, J. Chem. Phys. 1994, 100, 423; compare also: c) D. Schröder, S. Shaik, H. Schwarz, Acc. Chem. Res. 2000, 33, 139.
29. For examples of such calculations, see: a) J. N. Harvey, M. Aschi, H. Schwarz, W. Koch, Theor. Chem. Acc. 1998, 99, 95; b) S. Mitchell, M. Blitz, P, Siegbahn, M. Svensson, J. Chem. Phys. 1994, 100, 423; compare also: c) D. Schröder, S. Shaik, H. Schwarz, Acc. Chem. Res. 2000, 33, 139.
30. For examples of such calculations, see: a) J. N. Harvey, M. Aschi, H. Schwarz, W. Koch, Theor. Chem. Acc. 1998, 99, 95; b) S. Mitchell, M. Blitz, P, Siegbahn, M. Svensson, J. Chem. Phys. 1994, 100, 423; compare also: c) D. Schröder, S. Shaik, H. Schwarz, Acc. Chem. Res. 2000, 33, 139.