Organocatalytic Asymmetric Michael Reaction of Cyclic 1,3-Dicarbonyl Compounds and α,β-Unsaturated Ketones - A Highly Atom-Economic Catalytic One-Step Formation of Optically Active Warfarin Anticoagulant

Angewandte Chemie - International Edition

Volumn 42, Issue 40, 2003, Pages 4955-4957

  Halland, Nis ^a   Hansen, Tore ^a   Jørgensen, Karl Anker ^a  

^a AARHUS UNIVERSITY   (Denmark)

Author keywords

Asymmetric catalysis; Enones; Michael addition; Natural products; Synthetic methods

Indexed keywords

ADDITION REACTIONS; CATALYSIS; CRYSTALLIZATION; SYNTHESIS (CHEMICAL);

ORGANOCATALYSIS;

KETONES;

ANTICOAGULANT AGENT; CARBONYL DERIVATIVE; KETONE DERIVATIVE; WARFARIN;

ARTICLE; ASYMMETRIC CATALYSIS; CHEMICAL STRUCTURE; CRYSTALLIZATION; DRUG DESIGN; DRUG SYNTHESIS; ENANTIOSELECTIVITY; MICHAEL ADDITION; MOLECULAR DYNAMICS;

ANTICOAGULANTS; CATALYSIS; CYCLIZATION; KETONES; MODELS, MOLECULAR; MOLECULAR CONFORMATION; MOLECULAR STRUCTURE; STEREOISOMERISM; WARFARIN;

EID: 0242323633     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200352136     Document Type: Article

References (29)

1. For general reviews of asymmetric conjugate addition reactions, see: a) Comprehensive Asymmetric Catalysis, (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, Berlin, 1999;
2. b) M. P. Sibi, S. Manyem, Tetrahedron 2000, 56, 8033;
3. c) N. Krause, A. Hoffmann-Röder, Synthesis 2001, 171.
4. For example, see: a) R. A. O'Reilly, N. Engl. J. Med. 1976, 295, 354;
5. b) L. B. Wingard, R. A. O'Reilly, G. Levy, Clin. Pharmacol. Ther. 1978, 23, 212;
6. c) H. P. Rang, M. M. Dale, J. M. Ritter, P. Gardner, Pharmacology, 4th ed., Churchill Livingstone, Philadelphia, 2001.
7. H. J. Bardsley, A. K. Daly, PCT patent WO 00/43003, 2000.
8. A. S. Demir, C. Tanyeli, V. Gülbeyaz, H. Akgün, Turk. J. Chem. 1996, 20, 139.
9. See, for example: a) A. Robinson, H.-Y. Li, J. Feaster, Tetrahedron Lett. 1996, 37, 8321;
10. b) H.-Y. Li, A. Robinson, US patent 5, 856, 525, 1999.
11. G. Cravotto, G. M. Nano, G. Palmisano, S. Tagliapietra, Tetrahedron: Asymmetry 2001, 12, 707.
12. For iminium-ion-promoted asymmetric conjugate additions, see: a) S. P. Brown, N. C. Goodwin, D. W. C. MacMillan, J. Am. Chem. Soc. 2003, 125, 1192;
13. b) N. A. Paras, D. W. C. MacMillan, J. Am. Chem. Soc. 2002, 124, 7894;
14. c) N. A. Paras, D. W. C. MacMillan, J. Am. Chem. Soc. 2001, 123, 4370;
15. d) J. F. Austin, D. W. C. MacMillan, J. Am. Chem. Soc. 2002, 124, 1172;
16. e) N. Halland, P. S. Aburel, K. A. Jørgensen, Angew. Chem. 2003, 115, 685; Angew. Chem. Int. Ed. 2003, 42, 661;
17. e) N. Halland, P. S. Aburel, K. A. Jørgensen, Angew. Chem. 2003, 115, 685; Angew. Chem. Int. Ed. 2003, 42, 661;
18. f) N. Halland, R. G. Hazell, K. A. Jørgensen, J. Org. Chem. 2002, 67, 8331;
19. see also: g) M. Yamaguchi, T. Shiraishi, M. Hirama, J. Org. Chem. 1996, 61, 3520;
20. h) M. Yamaguchi, Y. Igarashi, R. S. Reddy, T. Shiraishi, M. Hirama, Tetrahedron 1997, 53, 11223;
21. i) M. Yamaguchi, T. Shiraishi, Y. Igarashi, M. Hirama, Tetrahedron Lett. 1994, 35, 8233;
22. j) M. Yamaguchi, T. Shiraishi, M. Hirama, Angew. Chem. 1993, 105, 1243; Angew. Chem. Int. Ed. Engl. 1993, 32, 1176;
23. j) M. Yamaguchi, T. Shiraishi, M. Hirama, Angew. Chem. 1993, 105, 1243; Angew. Chem. Int. Ed. Engl. 1993, 32, 1176;
24. k) A. Kawara, T. Taguchi, Tetrahedron Lett. 1994, 35, 8805.
25. Catalysts were formed by condensation of commercially available glyoxylic acid with the corresponding diamine (see Supporting Information).
26. CCDC-212540 and 212 541 contain the supplementary crystallographic data for this paper (1a and 1b, respectively). These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/ retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44) 1223-336-033; or deposit@ccdc.cam.ac.uk).
27. a) B. D. West, S. Preis, C. H. Schroeder, K. P. Link, J. Am. Chem. Soc. 1961, 83, 2676;
28. b) C. R. Wheeler, W. F. Trager, J. Med. Chem. 1979, 22, 1122.
29. PM3 calculations were performed by using the PC Spartan software. The alkene part in the hemiaminal species is significantly more activated (lower LUMO energy) towards nucleophilic addition than the alkene part in benzylideneacetone.