Ketones Baeyer-Villiger oxidations

For the oxidation of ketones, Baeyer-Villiger oxidation of cyclic ketones with monopersuccinic acid in water gives lactones in good results (Eq. 8.22).47 Peroxy species generated from borax in 30% hydrogen peroxide is effective for the Baeyer-Villiger oxidation of... 

Baeyer-Villiger Oxidation- oxidation of ketones to esters and lactones via oxygen insertion... 

The reaction of ketones with peroxy acids is both novel and synthetically useful An oxygen from the peroxy acid is inserted between the carbonyl group and one of the attached car bons of the ketone to give an ester Reactions of this type were first described by Adolf von Baeyer and Victor Vilhger m 1899 and are known as Baeyer—Villiger oxidations... 

Using Figure 17 15 as a guide write a mechanism for the ] Baeyer-Villiger oxidation of cyclohexyl methyl ketone by peroxybenzoic acid J... 

Baeyer-Villiger oxidation (Section 17 16) Oxidation of an aldehyde or more commonly a ketone with a peroxy acid The product of Baeyer-Vilhger oxidation of a ketone is an ester... 

The Baeyer-Villiger oxidation of ketones to esters (or lactones) occurs by the following mechanism. 

In a typical Knof procedure, 3jS-hydroxyandrost-5-en-17-one acetate is epoxidized with perbenzoic acid (or m-chloroperbenzoic acid ) to a mixture of 5a,6a- and 5)5,6)5-epoxides (75) in 99 % yield. Subsequent oxidation with aqueous chromium trioxide in methyl ethyl ketone affords the 5a-hydroxy-6-ketone (76) in 89% yield. Baeyer-Villiger oxidation of the hydroxy ketone (76) with perbenzoic acid (or w-chloroperbenzoic acid ) gives keto acid (77) in 96% yield as a complex with benzoic acid. The benzoic acid can be removed by sublimation or, more conveniently, by treating the complex with benzoyl chloride and pyridine to give the easily isolated )5-lactone (70) in 40% yield. As described in section III-A, pyrolysis of j5-lactone (70) affords A -B-norsteroid (71). Knof used this reaction sequence to prepare 3)5-hydroxy-B-norandrost-5-en-17-one acetate, B-noran-... 

Baeyer-Villiger oxidation by trifluoraperoxyacetic acid converts a chlo-rofluoroalkyl ketone into an ester 7l ] (equation 63)... 

FIGURE 17.15 Mechanism of the Baeyer-Villiger oxidation of a ketone. 

Section 17.16 The oxidation of ketones with peroxy acids is called the Baeyer-Villiger oxidation and is a useful method for preparing esters. 

Compounds known as lactones, which are cyclic esters, are formed on Baeyer—Villiger oxidation of cyclic ketones. Suggest a mechanism for the Baeyer—Villiger oxidation shown. 

Transformation of cyclic ketones into lactones by Baeyer-Villiger oxidation 99EJ0737. 

Transition metal catalysis in Baeyer-Villiger oxidation of cyclic ketones with formation of lactones 98AG(E)1198. 

When a ketone 1 is treated with hydrogen peroxyde or a peracid, a formal insertion of oxygen can take place to yield a carboxylic ester 2. This process is called the Baeyer-Villiger oxidation ... 

The Baeyer-Villiger oxidation is a synthetically very useful reaction it is for example often used in the synthesis of natural products. The Corey lactone 11 is a key intermediate in the total synthesis of the physiologically active prostaglandins. It can be prepared from the lactone 10, which in turn is obtained from the bicyclic ketone 9 by reaction with m-chloroperbenzoic acid (MCPBA) " ... 

The action of aqueous potassium hydroxide on chloronitrile 14 in DMSO at 25-30°C accomplishes the hydrolysis of the chloronitrile moiety and furnishes ketone 13 in a yield of 80%. Treatment of a solution of ketone 13 in CH2CI2 with mCPBA and sodium bicarbonate results in a selective Baeyer-Villiger oxidation to give bicyclic lactone 12 in >95% yield. It is noteworthy that the Baeyer-Villiger oxidation is completely regioselective and that the... 

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