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

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

Journal

Advanced Synthesis & Catalysis
ISSN: 1615-4169 , E-ISSN: 1615-4150

Output data

Year: 2019, Volume: 361, Number: 13, Pages: 3173-3181 Pages count : 9 DOI: 10.1002/adsc.201900271

Authors

Vil' Vera A. ¹ , Gorlov Evgenii S. ^2,1 , Bityukov Oleg V. ¹ , Barsegyan Yana A. ¹ , Romanova Yulia E. ^2,1 , Merkulova Valentina M. ¹ , Terent'ev Alexander O. ^2,1

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, Moscow, 119991 Russian Federation
2	D. I. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Square, Moscow, 125047 Russian Federation

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.

Vil' V.A. , Gorlov E.S. , Bityukov O.V. , Barsegyan Y.A. , Romanova Y.E. , Merkulova V.M. , Terent'ev A.O.
C−O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non‐Rubottom Oxidation
Advanced Synthesis & Catalysis. 2019. V.361. N13. P.3173-3181. DOI: 10.1002/adsc.201900271 WOS Scopus OpenAlex

Web of science:	WOS:000484142600017
Scopus:	2-s2.0-85065328673
OpenAlex:	W2935308669

DB	Citing
OpenAlex	17
Scopus	18