Catalytic asymmetric hydrosilylation of ketones using rhodium-(I)-complexes of chiral phosphinooxazoline ligands

Tetrahedron Asymmetry

Volumn 7, Issue 6, 1996, Pages 1599-1602

  Langer, Thomas ^a   Janssen, Jörg ^a   Helmchen, Günter ^a  

^a UNIVERSITY OF HEIDELBERG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ACETOPHENONE; KETONE; OXAZOLINE DERIVATIVE; RHODIUM;

ARTICLE; BINDING AFFINITY; CATALYSIS; CHELATION; ENANTIOMER; HYDROXYLATION; LIGAND BINDING; PRIORITY JOURNAL;

EID: 0029976471     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/0957-4166(96)00192-9     Document Type: Article

References (19)

1. G. Helmchen, A. Krotz, K.-T. Ganz, D. Hansen, Synlett 1991, 257-259.
2. Most of the results reported here are taken from: T. Langer, Dissertation, Univ. Heidelberg, 1995.
3. For reviews see: (a) I. Ojima, K. Hirai, in Asymmetric Synthesis, J.D. Morrison, Ed., Vol. 5, pp 103-146, Academic, Orlando 1985;
4. (b) H. Brunner in Houben-Weyl, Stereoselective Synthesis, G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann, Eds., Vol E 21, pp 4074-4081, Thieme, Stuttgart, 1995, and references therein.
5. (a) S. Uemura, Y. Nishibayashi, K. Segawa, J. D. Singh, S. Fukuzawa, K. Ohe, Organometallics 1996, 15, 370-379;
6. (b) Y. Nishibayashi, K. Segawa, H. Hiroya, K. Ohe, S. Uemura, Chem. Commun. 1996, 847-848.
7. (c) S. Uemura, Y. Nishibayashi, K. Segawa, K. Ohe, Organometallics 1995, 14, 5486-5487;
8. (d) T. Hyashi, C. Hayashi, Y. Uozumi, Tetrahedron: Asymmetry 1995, 6, 2503-2506;
9. (e) H. Brunner, C. Henrichs; Tetrahedron: Asymmetry 1995, 6, 653-656;
10. (f) Y. Ito, M. Sawamura, R. Kuwano, J. Shirai, Synlett 1995, 347-348;
11. (g) J. W. Faller, K. J. Chase; Organometallics 1994, 13, 989-992;
12. (h) R. L. Haltermann, T. M. Ramsey, Z. Chen, J. Org. Chem. 1994, 59, 2642-2644;
13. (i) Y. Ito, M. Sawamura, Y. Kuwano, Angew. Chem. 1994, 106, 92-93: Int. Ed. Engl. 1994, 33, 111-112.
14. (i) Y. Ito, M. Sawamura, Y. Kuwano, Angew. Chem. 1994, 106, 92-93: Int. Ed. Engl. 1994, 33, 111-112.
15. Preparation of phosphinooxazolines: M. Peer, J.C. de Jong, M. Kiefer, Th. Langer, H. Rieck, H. Schell, P. Sennhenn, J. Sprinz, H. Steinhagen, B. Wiese, G. Helmchen, Tetrahedron, in print, and work of other groups cited therein.
16. T. Masuda, J. K. Stille, J. Am. Chem. Soc. 1978, 100, 268-272.
17. The reaction can be carried out even at -78°C, but with 2 mol% of Rh and 10 mol% of ligand: L. M. Newman, J. M. J. Williams, R. McCague, G. A. Potter, Tetrahedron: Asymmetry, accompanying article.
18. 4 and concentrated in vacuo. The residue was subjected to bulb-to-bulb distillation (0.2 mm Hg, 130-150°C). In the case of ethyl levulinate as substrate, the reaction was maintained for 68 h at room temperature and stopped by addition of 2 ml of a 1% solution of p-toluenesulfonic acid in methanol. After further work-up as discribed above γ-valerolactone was obtained as product and was characterized.
19. Synthesis cf ligand 10: N. Schmees, Diplomarbeit, Univ. Heidelberg 1995.