C−O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non‐Rubottom Oxidation.

Autor: Vil', Vera A., Gorlov, Evgenii S., Bityukov, Oleg V., Barsegyan, Yana A., Romanova, Yulia E., Merkulova, Valentina M., Terent'ev, Alexander O.
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Zdroj: Advanced Synthesis & Catalysis; Jul2019, Vol. 361 Issue 13, p3173-3181, 9p
Abstrakt: Malonyl peroxides act both as oxidants and reagents for C−O coupling in reactions with methyl and silyl enol ethers. In the proposed conditions, the oxidative C−O coupling of malonyl peroxides with enol ethers selectively proceeds, bypassing the traditional Rubottom hydroxylation of enol ethers by peroxides. It was observed that the oxidative [5+2] cycloaddition of malonyl peroxides and enol ethers is the key stage of the discovered process. Oxidative C−O coupling of silyl enol ethers leads to the formation of α‐acyloxyketones with a free carboxylic acid group. A specially developed preparative one‐pot procedure transforms ketones via silyl enol ethers formation and the following coupling into α‐acyloxyketones with yields 35–88%. The acid‐catalyzed coupling with methyl enol ethers gives remarkable products while retaining the easily oxidizable enol fragment. Furthermore, these molecules contain a free carboxylic acid group, thus these nontrivial products contain two usually incompatible acid and enol ether groups. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index
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