Oxidation Prilezhaev

Related reactions Davis oxaziridine oxidation, Prilezhaev reaction, Sharpless asymmetric epoxidation, Shi asymmetric epoxidation ... 

Peracids react heterolytically with olefins with the formation of epoxides by the Prilezhaev reaction. So, the co-oxidation of aldehydes with olefins has technological importance. Peracids react with ketones with formation of lactones. These reactions will be discussed in Section 8.2. The oxidation of aldehydes are discussed in monographs [4-8]. 

The reaction of olefin epoxidation by peracids was discovered by Prilezhaev [235]. The first observation concerning catalytic olefin epoxidation was made in 1950 by Hawkins [236]. He discovered oxide formation from cyclohexene and 1-octane during the decomposition of cumyl hydroperoxide in the medium of these hydrocarbons in the presence of vanadium pentaoxide. From 1963 to 1965, the Halcon Co. developed and patented the process of preparation of propylene oxide and styrene from propylene and ethylbenzene in which the key stage is the catalytic epoxidation of propylene by ethylbenzene hydroperoxide [237,238]. In 1965, Indictor and Brill [239] published studies on the epoxidation of several olefins by 1,1-dimethylethyl hydroperoxide catalyzed by acetylacetonates of several metals. They observed the high yield of oxide (close to 100% with respect to hydroperoxide) for catalysis by molybdenum, vanadium, and chromium acetylacetonates. The low yield of oxide (15-28%) was observed in the case of catalysis by manganese, cobalt, iron, and copper acetylacetonates. The further studies showed that molybdenum, vanadium, and... 

NA Prilezhaev. Organic Peroxides and their Application for Oxidation of Unsaturated Compounds. Warsaw, 1912 [in Russian]. 

Direct Oxidation with Stoichiometric Oxidants. Discovered by Prilezhaev in 1909,211 the typical epoxidation reaction of alkenes is their oxidation with organic peracids. Of the large number of different peroxycarboxylic acids used in... 

E. N. Prilezhaeva, Prilezhaev Reaction, Electrophilic Oxidation, Nauka, Moscow, U.S.S.R., 1974. 

Prilezhaev reaction Oxidation of alkenes to epoxides using peroxycarboxylic acids. 362... 

Related reactions Jacobsen-Katsuki epoxidation, Prilezhaev oxidation, Rubottom oxidation, Sharpless asymmetric epoxidation, Shi... 

Prilezhaev, N. Oxidation of Unsaturated Compounds by Means of Organic Peroxides. Ber. 1909,42,4811-4815. 

Prilezhaev Epoxidation, Prileschajew Epoxidation, Prilezhaev Oxidation)... 

Strategic exploitation of the molecular shape of lactone 309 was next utilized to install the desired stereogenicity at all positions on tricychc compound 311, a key intermediate targeted as the substrate for a reductive cyclization cascade. The quaternary center at the lactone a-position was first addressed. Deprotonation with hthium diisopropylamide in THF and addition of 1-cyanobenzotriazole (BtCN) yielded an a-cyanolactone, which was then alkylated from the convex face of the molecule employing ethyl iodide in a mixture of warm acetonitrile and potassium carbonate to furnish lactone 310. The scaffold curvature was then exploited to epoxidize stereoselec-tively the double bond from the convex face to provide oxirane 311 following a Prilezhaev oxidation protocol. 

Prilezhaev reaction (epoxidation of olefins) Additive oxidation... 

Prilezhaev, E. N. Prilezhaev Reaction. Electrophilic oxidation, Moscow, Nauka , 1974, (In Russian),... 

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