Silyl enol ethers Rubottom oxidation

Unique successful hydroxylations with ozone and mCPBA First Successful Method Epoxidation of Silyl Enol Ethers (Rubottom Oxidation) Method, mechanism, and isolation of intermediates Chemo- regio- and stereoselectivity synthesis of fused y-laclones Hydroxylation of Amino-ketones via Silyl Enol Ethers Synthesis of vinca alkaloids and model compounds... 

First Successful Method Epoxidation of Silyl Enol Ethers (Rubottom Oxidation)... 

Hegedus and co-workers isolated a cyclobutane-fused epoxide intermediate in the Rubottom oxidation of silyl enol ether 17 (Scheme 9) <1998JOC4691>. 

Jauch, J. Stereochemistry of the Rubottom oxidation with bicyclic silyl enol ethers synthesis and dimerization reactions of bicyclic a-hydroxy ketones. Tetrahedron 1994, 50,12903-12912. 

In 1958, Rubottom and co-workers introduced an oxidative methodology, which first requires the conversion of a carbonyl compound to either an enol silane or silyl enol ether. As generated, the enol silane 3, for example, is then treated with m-chloroperbenzoic acid (m-CPBA) to form the a-hydroxy carbonyl compound 4 following epoxidation and desilylation.3... 

Silyl enol ethers are a class of electron-rich, nonaromatic compounds that easily form reactive radical cations on one electron oxidation. The silyl enol ether functional group is closely related to the carbonyl function and consequently, syntheses of silyl enol ethers generally make use of enolates. In addition, silyl enol ethers can be described as masked enols or enolates since their reactions often yield ketones. A number of oxidation reactions of silyl enol ethers making use of oxygen or oxygen-containing reagents such as peroxides, peracids (known as Rubottom oxidation), dioxirane, osmium tetraoxide, or triphenyl phosphite ozonide have been described in the literature. In all cases either a-hydroxy-ketones or the silyl enol ether epoxides are formed. 

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