Acyloxylation of 1-Methoxycyclohex-1-ene and Other Enol Ethers with Dimethyl Peroxydicarbonate

Schank, Kurt; Beck, H. P.; Pistorius, Susanne; Rapold, Thomas

doi:10.1055/s-1995-4026

Cited by 5 publications

(2 citation statements)

References 8 publications

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“…Two related processes are known. First, the oxidation of enol ethers by dimethyl peroxydicarbonate resulted in the introduction of methylcarbonate group in α‐position . Second, the reaction of lithium enolates and enol ethers with dibenzyl peroxydicarbonate forms α‐benzyloxycarbonyl ketones .…”

Section: Resultsmentioning

confidence: 97%

“…First, the oxidation of enol ethers by dimethyl peroxydicarbonate resulted in the introduction of methylcarbonate group in α-position. [67] Second, the reaction of lithium enolates and enol ethers with dibenzyl peroxydicarbonate forms α-benzyloxycarbonyl ketones. [68] It should be noted that the presented method makes the α-oxygenated ketones with the pendant carboxylic-acid functionality in the α-acyloxy substituent.…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2019

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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.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%