Oxidation of olefins to ketones

SCHEME 139. Oxidation of olefins to ketones with palladium catalyst 215 in a perfluorinated solvent... 

Harada, A., Hu. Y. and Takahashi. S. (1986) Cyclodextrin-paJJadium chloride. New catalytic system for selective oxidation of olefins to ketones. Chem. Lett., 2083-2084. 

Rhodium(II) acetate catalyzes C—H insertion, olefin addition, heteroatom-H insertion, and ylide formation of a-diazocarbonyls via a rhodium carbenoid species (144—147). Intramolecular cyclopentane formation via C—H insertion occurs with retention of stereochemistry (143). Chiral rhodium (TT) carboxamides catalyze enantioselective cyclopropanation and intramolecular C—N insertions of CC-diazoketones (148). Other reactions catalyzed by rhodium complexes include double-bond migration (140), hydrogenation of aromatic aldehydes and ketones to hydrocarbons (150), homologation of esters (151), carbonylation of formaldehyde (152) and amines (140), reductive carbonylation of dimethyl ether or methyl acetate to 1,1-diacetoxy ethane (153), decarbonylation of aldehydes (140), water gas shift reaction (69,154), C—C skeletal rearrangements (132,140), oxidation of olefins to ketones (155) and aldehydes (156), and oxidation of substituted anthracenes to anthraquinones (157). Rhodium-catalyzed hydrosilation of olefins, alkynes, carbonyls, alcohols, and imines is facile and may also be accomplished enantioselectively (140). Rhodium complexes are moderately active alkene and alkyne polymerization catalysts (140). In some cases polymer-supported versions of homogeneous rhodium catalysts have improved activity, compared to their homogenous counterparts. This is the case for the conversion of alkenes direcdy to alcohols under oxo conditions by rhodium—amine polymer catalysts... 

J. Tsuji, Synthetic Applications of the Palladium-Catalysed Oxidation of Olefins to Ketones, Synthesis 1984, 369. 

Review "Synthetic Applications of the Palladium Catalyzed Oxidation of Olefins to Ketones"... 

Very few examples of the oxidation of olefins to ketones in ionic liquids have been reported. In one case, [C4Ciim][BF4] or [C4Ciim][PF6] were used in the palladium-catalysed oxidation of styrene to acetophenone with H2O2 as oxidant, however the concept of biphasic catalysis was not exploited and no attempts were made to recycle the catalyst.[131 The ionic liquid serves the purpose of a co-catalyst rather than that of a reaction medium. 

Tsuji, J. 1984. Synthetic applications of the palladium-catalyzed oxidation of olefins to ketones. Synthesis 369-383. 

M. Perree-Fauvet, A. Gaudemer, Manganese porphyrin-catalysed oxidation of olefins to ketones by molecular oxygen, /. Chem. Soc. Chem. Commun. (1981) 874. 

Wacker oxidation of olefins to ketones catalyzed by palladium complexes is a well-known process which has been applied to numerous olefins [120]. However, selective oxidation of Cg-Cig a-olefins remains a challenge. Recently, Mortreux et al. have developed a new catalytic system for the quantitative and selective oxidation of higher a-olefins in an aqueous medium [121-123]. For example, 1-decene was oxidized to 2-decanone in 98% yield using PdS04/ H9PV6M06O40/CUSO4 as the catalyst in the presence of per(2,6-di-0-methyl)-j9-cyclodextrin, which probably played the role of a reverse phase transfer reagent [Eq. (22)]. 

WACKER - T S U JI Olefin oxidation Oxidation of olefins to ketones by Pd (II) catalyst... 

Andrews MA, Kelly KP (1981) The transition-metal nitro-nitrosyl redox couple - catalytic-oxidation of olefins to ketones. J Am Chem Soc 103 2894—2896... 

Catalytic oxidation of olefins to ketones and aldehydes 3.2.1. Wacker type oxidation of olefins... 

Oxidation of olefins to ketones by palladium chloride and an inorganic (cupric ions) or organic (benzoquinone) co-oxidizer is an effective method which has been applied for a long time. It was used in the regioselective preparation of a lipidic ketone, from an olefinic azide, without disturbance of the latter group (Fig. 35) 38... 

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