Silyl enol ether

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The general structure of a silyl enol ether

Silyl enol ethers in organic chemistry are a class of organic compounds sharing a common functional group comprised of an enolate bonded through its oxygen terminus to an organosilicon group.

Silyl enol ethers are important intermediates in organic synthesis.

Organic synthesis


Organic reactions

Silyl enol ethers react as nucleophiles in:

Saegusa oxidation

In the Saegusa oxidation certain silyl enol ethers are oxidized to enones with palladium(II) acetate. In the original publication [5] the amount of palladium is less than stochiometric and 1,4-benzoquinone is used as sacrificial catalyst. The intermediate is an oxo-allylpalladium complex.

Saegusa oxidation

In one application an dienenone is synthesized in two steps from a cyclohexanone [6] [7]:

Saegusa application Clive 2007

References

  1. Organic Syntheses, Coll. Vol. 9, p.564 (1998); Vol. 73, p.123 (1996) Article
  2. Organic Syntheses, Coll. Vol. 8, p.277 (1993); Vol. 66, p. 43 (1988) Article.
  3. Organic Syntheses, Coll. Vol. 8, p.286 (1993); Vol. 69, p.129 (1990) Article
  4. Organic Syntheses, Coll. Vol. 7, p.282 (1990); Vol. 64, p.118 (1986) Article.
  5. 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
  6. 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
  7. reagents in step 1 are trimethylsilyl triflate and 2,6-lutidine



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