Silyl enol ether
Silyl enol ethers are important intermediates in organic synthesis.
- Trimethylsilyl enol ethers can be prepared from ketones in presence of a strong base and trimethylsilyl chloride.
- Silyl enol ether can form by capturing any enolate formed in a nucleophilic conjugate addition.
Silyl enol ethers react as nucleophiles in:
- Aldol reactions
- Michael reactions
- Haloketone formation with halogens
- Acyloin formation by organic oxidation with mCPBA
In the Saegusa oxidation certain silyl enol ethers are oxidized to enones with palladium(II) acetate. In the original publication  the amount of palladium is less than stochiometric and 1,4-benzoquinone is used as sacrificial catalyst. The intermediate is an oxo-allylpalladium complex.
- Organic Syntheses, Coll. Vol. 9, p.564 (1998); Vol. 73, p.123 (1996) Article
- Organic Syntheses, Coll. Vol. 8, p.277 (1993); Vol. 66, p. 43 (1988) Article.
- Organic Syntheses, Coll. Vol. 8, p.286 (1993); Vol. 69, p.129 (1990) Article
- Organic Syntheses, Coll. Vol. 7, p.282 (1990); Vol. 64, p.118 (1986) Article.
- Synthesis of alpha,beta-unsaturated carbonyl compounds by palladium(II)-catalyzed dehydrosilylation of silyl enol ethers Yoshihiko Ito, Toshikazu Hirao, and Takeo Saegusa J. Org. Chem.; 1978; 43(5) pp 1011 - 1013; doi:10.1021/jo00399a052
- Formation of Benzo-Fused Carbocycles by Formal Radical Cyclization onto an Aromatic Ring Derrick L. J. Clive and Rajesh Sunasee Org. Lett.; 2007; 9(14) pp 2677 - 2680; (Letter) doi:10.1021/ol070849l
- reagents in step 1 are trimethylsilyl triflate and 2,6-lutidine