Rubottom Oxidation

The synthesis of α-hydroxy ketones is achieved by reaction of silyl enol ethers with mCPBA, with subsequent rearrangement. Aqueous work up or reaction with TBAF (fluoride ions) gives the desired product after desilylation

---

Mechanism of the Rubottom Oxidation

The enol ether double bond is epoxidized by the peracid. Relief of the epoxide ring strain drives the rearrangement with migration of the silyl group to give the silylated α-hydroxy ketone product.

Recent Literature

Aza-Rubottom Oxidation: Synthetic Access to Primary α-Aminoketones
Z. Zhou, Q.-Q. Cheng, L. Kürti, J. Am. Chem. Soc., 2019, 141, 2242-2246.

Oxidation of Methyl Trimethylsilyl Ketene Acetals to α-Hydroxyesters with Urea Hydrogen Peroxide Catalyzed by Methyltrioxorhenium
S. Stanković, J. H. Espenson, J. Org. Chem., 2000, 65, 5528-5530.