A Highly Active and Selective Catalyst System for the Baylis-Hillman Reaction

Angewandte Chemie - International Edition

Volumn 42, Issue 41, 2003, Pages 5054-5056

  You, Jingsong ^a   Xu, Juhua ^a   Verkade, John G ^a  

^a IOWA STATE UNIVERSITY   (United States)

Author keywords

Baylis Hillman reaction; Heterocycles; Lewis bases; Titanium

Indexed keywords

ALDEHYDES; ELECTRONS; REACTION KINETICS; SULFUR;

COCATALYSTS;

CATALYST SELECTIVITY;

ANISALDEHYDE; NITROGEN; PHOSPHORUS; SULFUR; TITANIUM CHLORIDE; TITANIUM DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; BAYLIS HILLMAN REACTION; CATALYSIS; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; COMPLEX FORMATION; REACTION ANALYSIS; ROOM TEMPERATURE; STEREOSPECIFICITY; STRUCTURE ANALYSIS;

EID: 0242291878     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200352233     Document Type: Article

References (41)

1. For recent reviews see: a) D. Basavaiah, A. J. Rao, T. Satyanarayana, Chem. Rev. 2003, 103, 811-891, and references therein;
2. b) P. Langer, Angew. Chem. 2000, 112, 3177-3180; Angew. Chem. Int. Ed. 2000, 39, 3049-3052.
3. b) P. Langer, Angew. Chem. 2000, 112, 3177-3180; Angew. Chem. Int. Ed. 2000, 39, 3049-3052.
4. a) S. Matsumoto, Y. Okubo, K. Mikami, J. Am. Chem. Soc. 1998, 120, 4015-4016;
5. b) Y. Fort, M. C. Berthe, P. Caubere, Tetrahedron 1992, 48, 6371-6384.
6. a) C. Yu, B. Liu, L. Hu, J. Org. Chem. 2001, 66, 5413-5418;
7. b) W.-D. Lee, K.-S. Yang, K. Chen, Chem. Commun. 2001, 1612-1613;
8. c) J. Cai, Z. Zhou, G. Zhao, C. Tang, Org. Lett. 2002, 4, 4723-4725;
9. d) V. K. Aggarwal, D. K. Dean, A. Mereu, R. Williams, J. Org. Chem. 2002, 67, 510-514;
10. e) C. Yu, L. Hu, J. Org. Chem. 2002, 67, 219-223;
11. f) V. K. Aggarwal, I. Emme, S. Y. Fulford, J. Org. Chem. 2003, 68, 692-700.
12. a) W. Pei, H.-X. Wei, G. Li, Chem. Commun. 2002, 1856-1857;
13. b) W. Pei, H.-X. Wei, G. Li, Chem. Commun. 2002, 2412-2413;
14. c) D. Balan, H. Adolfsson, J. Org. Chem. 2002, 67, 2329-2334;
15. d) V. K. Aggarwal, A. Mereu, G. J. Tarver, R. McCague, J. Org. Chem. 1998, 63, 7183-7189;
16. e) K. Yang, W. Lee, J. Pan, K. Chen, J. Org. Chem. 2003, 68, 915-919;
17. f) T. Iwamura, M. Fujita, T. Kawakita, S. Kinoshita, S. Watanabe, T. Kataoka, Tetrahedron 2001, 57, 8455-8462;
18. g) M. Shi, C. Wang, Helv. Chim. Acta 2002, 85, 841-846.
19. a) G. Li, H.-X. Wei, J. J. Gao, T. D. Caputo, Tetrahedron Lett. 2000, 41, 1-5;
20. b) A. Patra, S. Batra, B. S. Joshi, R. Roy, B. Kundu, A. P. Bhaduri, J. Org. Chem. 2002, 67, 5783-5788.
21. a) T. Kataoka, T. Iwama, S. Tsujiyama, Chem. Commun. 1998, 197-198;
22. b) T. Kataoka, T. Iwama, S. Tsujiyama, T. Iwamura, S. Watanabe, Tetrahedron 1998, 54, 11813-11824;
23. c) T. Iwama, H. Kinoshita, T. Kataoka, Tetrahedron Lett. 1999, 40, 3741-3744;
24. d) T. Kataoka, H. Kinoshita, T. Iwama, S. Tsujiyama, T. Iwamura, S. Watanabe, O. Muraoka, G. Tanabe, Tetrahedron 2000, 56, 4725-4731;
25. e) T. Kataoka, H. Kinoshita, S. Kinoshita, T. Iwamura, S. Watanabe, Angew. Chem. 2000, 112, 2448-2450; Angew. Chem. Int. Ed. 2000, 39, 2358-2360.
26. e) T. Kataoka, H. Kinoshita, S. Kinoshita, T. Iwamura, S. Watanabe, Angew. Chem. 2000, 112, 2448-2450; Angew. Chem. Int. Ed. 2000, 39, 2358-2360.
27. a) S. Uehira, Z. Han, H. Shinokubo, K. Oshima, Org. Lett. 1999, 1, 1383-1385;
28. b) M. Shi, J.-K. Jiang, Tetrahedron 2000, 56, 4793-4797;
29. c) M. Shi, J.-K. Jiang, Y.-S., Feng, Org. Lett. 2000, 2, 2397-2400;
30. d) M. Shi, Y.-S. Feng, J. Org. Chem. 2001, 66, 406-411;
31. e) G. Li, J. Gao, H.-X. Wei, M. Enright, Org. Lett. 2000, 2, 617-620.
32. a) J. G. Verkade, Top. Curr. Chem. 2003, 233, 1-44, and references therein;
33. b) P. B. Kisanga, J. G. Verkade, Tetrahedron Reports, 2003, in press.
34. P. B. Kisanga, J. G. Verkade, J. Org. Chem. 2002, 67, 426-430.
35. An excess of α,β-unsaturated ketone required for complete consumption of aldehyde and optimized yields.
36. 4 and concentrated in vacuo to give the crude product, which was purified by column chromatography on silica gel (ethyl acetate/hexane 1:3).
37. S. K. Xi, H. Schmidt, C. Lensink, S. Kim, D. Wintergrass, L. M. Jacobson, J. G. Verkade, Inorg. Chem. 1990, 29, 2214-2220.
38. L. M. Walsh, C. L. Winn, J. M. Goodman, Tetrahedron Lett. 2002, 43, 8219-8222.
39. Under the same conditions the reaction of methyl vinyl ketone with p-nitrobenzaldehyde gave the BH adduct in 75 % yield.
40. Attempts to detect this intermediate by NMR spectroscopy have thus far failed.
41. Electron-rich aromatic aldehydes such as anisaldehyde do not provide BH adducts when a more sterically hindered 3-substituted cyclohex-2-en-1-one is used.