Iminoxyl radicals vs. tert-butylperoxyl radical in competitive oxidative C-O coupling with beta-dicarbonyl compounds. Oxime ether formation prevails over Kharasch peroxidation
Krylov, IB; Paveliev, SA; Shumakova, NS; Syroeshkin, MA; Shelimov, BN; Nikishin, GI; Terent'ev, AO
| HERO ID | 4854525 |
|---|---|
| In Press | No |
| Year | 2018 |
| Title | Iminoxyl radicals vs. tert-butylperoxyl radical in competitive oxidative C-O coupling with beta-dicarbonyl compounds. Oxime ether formation prevails over Kharasch peroxidation |
| Authors | Krylov, IB; Paveliev, SA; Shumakova, NS; Syroeshkin, MA; Shelimov, BN; Nikishin, GI; Terent'ev, AO |
| Journal | RSC Advances |
| Volume | 8 |
| Issue | 11 |
| Page Numbers | 5670-5677 |
| Abstract | Oxidative coupling of oxime and beta-dicarbonyl compounds dominates in a beta-dicarbonyl compound/oxime/Cu(II)/t-BuOOH system; in the absence of oxime, oxidative coupling of t-BuOOH and a beta-dicarbonyl compound (Kharasch peroxidation) takes place. The proposed conditions for oxidative coupling of oximes with dicarbonyl compounds require only catalytic amounts of copper salt and t-BuOOH serves as a terminal oxidant. The C-O coupling reaction proceeds via the formation of tert-butoxyl, tert-butylperoxyl and iminoxyl radicals. Apparently, tert-butylperoxyl radicals oxidize oxime into iminoxyl radical faster than they react with beta-dicarbonyl compounds forming the Kharasch peroxidation product. Iminoxyl radicals are responsible for the formation of the target C-O coupling products; the yields are up to 77%. |
| Doi | 10.1039/c7ra13587d |
| Wosid | WOS:000424465500004 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |