Pd(OH)2/C-mediated selective oxidation of silyl enol ethers by tert-butylhydroperoxide, a useful method for the conversion of ketones to α,β-enones or β-Silyloxy-α,β-enones

Organic Letters

Volumn 7, Issue 7, 2005, Pages 1415-1417

  Yu, Jin Quan ^b,c   Wu, Hai Chen ^c   Corey, E J ^a  

^a HARVARD UNIVERSITY   (United States)

^b BRANDEIS UNIVERSITY   (United States)

^c UNIVERSITY OF CAMBRIDGE   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

KETONE DERIVATIVE; PALLADIUM COMPLEX; SILANE DERIVATIVE; TERT BUTYL HYDROPEROXIDE;

ARTICLE; CATALYSIS; OXIDATION;

EID: 17444428665     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol050284y     Document Type: Article

References (17)

1. See: (a) Stankovic, S.; Espenson, J. H. J. Org. Chem. 1998, 63, 4129. (b) Adam, W.; Fell, R. T.; Saha-Moller, C. R.; Zhao, C. G. Tetrahedron: Asymmetry 1998, 9, 397. (c) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708. (d) Ryter, K.; Livinghouse, T. J. Am. Chem. Soc. 1998, 120, 2658. (e) Yamamoto, H.; Tsuda, M.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 1997, 62, 7174.
2. See: (a) Stankovic, S.; Espenson, J. H. J. Org. Chem. 1998, 63, 4129. (b) Adam, W.; Fell, R. T.; Saha-Moller, C. R.; Zhao, C. G. Tetrahedron: Asymmetry 1998, 9, 397. (c) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708. (d) Ryter, K.; Livinghouse, T. J. Am. Chem. Soc. 1998, 120, 2658. (e) Yamamoto, H.; Tsuda, M.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 1997, 62, 7174.
3. See: (a) Stankovic, S.; Espenson, J. H. J. Org. Chem. 1998, 63, 4129. (b) Adam, W.; Fell, R. T.; Saha-Moller, C. R.; Zhao, C. G. Tetrahedron: Asymmetry 1998, 9, 397. (c) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708. (d) Ryter, K.; Livinghouse, T. J. Am. Chem. Soc. 1998, 120, 2658. (e) Yamamoto, H.; Tsuda, M.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 1997, 62, 7174.
4. See: (a) Stankovic, S.; Espenson, J. H. J. Org. Chem. 1998, 63, 4129. (b) Adam, W.; Fell, R. T.; Saha-Moller, C. R.; Zhao, C. G. Tetrahedron: Asymmetry 1998, 9, 397. (c) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708. (d) Ryter, K.; Livinghouse, T. J. Am. Chem. Soc. 1998, 120, 2658. (e) Yamamoto, H.; Tsuda, M.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 1997, 62, 7174.
5. See: (a) Stankovic, S.; Espenson, J. H. J. Org. Chem. 1998, 63, 4129. (b) Adam, W.; Fell, R. T.; Saha-Moller, C. R.; Zhao, C. G. Tetrahedron: Asymmetry 1998, 9, 397. (c) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708. (d) Ryter, K.; Livinghouse, T. J. Am. Chem. Soc. 1998, 120, 2658. (e) Yamamoto, H.; Tsuda, M.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 1997, 62, 7174.
6. Ito, Y.; Hirao, T.; Saegusa, T. J. Org. Chem. 1978, 43, 1011.
7. Nicolaou, K. C.; Gray, D. L. F.; Montagnon, T.; Harrison, S. T. Angew. Chem., Int. Ed. 2002, 41, 996.
8. (a) Yu, J. Q.; Corey, E. J. Org. Lett. 2002, 4, 2727.
9. (b) Yu, J. Q.; Corey, E. J. J. Am. Chem. Soc. 2003, 125, 3232.
10. Also, for a recent example of Rh(I)-catalyzed allylic oxidation by t-BuOOH, see: Catino, A. J.; Forslund, R. E.; Doyle, M. P. J. Am. Chem. Soc. 2004, 126, 13622.
11. See: (a) Zhang, Y.; Raines, A. J.; Flowers, R. A., II. Org. Lett. 2003, 5, 2363. (b) House, H. O.; Rasmusson, G. H. J. Org. Chem. 1963, 28, 27. (c) Takahashi, K.; Tanaka, T.; Suzuki, T.; Hirama, M. Tetrahedron 1994, 50, 1327.
12. See: (a) Zhang, Y.; Raines, A. J.; Flowers, R. A., II. Org. Lett. 2003, 5, 2363. (b) House, H. O.; Rasmusson, G. H. J. Org. Chem. 1963, 28, 27. (c) Takahashi, K.; Tanaka, T.; Suzuki, T.; Hirama, M. Tetrahedron 1994, 50, 1327.
13. See: (a) Zhang, Y.; Raines, A. J.; Flowers, R. A., II. Org. Lett. 2003, 5, 2363. (b) House, H. O.; Rasmusson, G. H. J. Org. Chem. 1963, 28, 27. (c) Takahashi, K.; Tanaka, T.; Suzuki, T.; Hirama, M. Tetrahedron 1994, 50, 1327.
14. Bhosale, R. S.; Bhosale, S. V.; Bhosale, S. V.; Wang, T.; Zubaidha, P. K. Tetrahedron Lett. 2004, 45, 7187.
15. General Procedure for the Preparation of Silyl Enol Ethers. Triisopropylsilyl triflate (1.84 g, 6.0 mmol) was added to a solution of the ketone (5.0 mmol) and triethylamine (0.91 g, 9.0 mmol) in dichloromethane (15 mL). The progress of the reaction was monitored by TLC, and when the reaction was complete, the mixture was diluted with dichoromethane and washed with cold sodium bicarbonate. After the organic layer was dried over anhydrous sodium sulfate and concentrated on a rotovap, the residue was taken up in dry ether and separated from the insoluble triethylammonium triflate. The ether solution was then concentrated and chromatographed on basic alumina (pH 9.0-9.5) using pure hexane as an eluent to give the pure product.
16. 2. After removal of the solvent by rota-evaporation at 24°C, the crude product was purified by flash column chromatography (ether-hexane, 1:1) to provide the analytically pure sample as a clear oil.
17. 2. After removal of the solvent by rotaevaporation at 24°C, the crude product was purified by flash column chromatography (ether-hexane, 1: I) to provide the analytically pure sample as a clear oil.