Olefin Oxidations Related to the Wacker Process

The oxidation of higher olefins has also been studied, and these reactions form ketones (Equation 16.102). Thus, the C-0 bond formation between water and the substituted olefin mediated by palladium occurs at flie internal carbon. For example, paUadium-catalyzed oxidation of propene forms acetone, and this reaction provides one industrial route to this material. Oxidations of substituted olefins to form ketones have also become a common method for the conversion of olefins to ketones during complex-molecule synthesis. Examples of the use of palladium-catalyzed oxidation in complex-molecule synthesis are described later in this chapter. 

The oxidations of olefins with many oxygen nucleophiles other than water have also been reported. These reactions include the s5mthesis of vinylic and allylic ethers from reactions of olefins with alcohols and phenols, and vinylic and allylic esters from reactions of olefins with carboxylic acids. These reactions have been conducted with both monoenes and 1,3-dienes. Both intermolecular and intramolecular versions of each of these processes have been developed. Some discussion of these reactions was included in Chapter 11 because of their connection to the nucleophilic attack of oxygen nucleophiles on coordinated olefins and dienes. 

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Some olefin oxidations related to the Wacker process are given in Eqs. (103) and (104) (Lloyd and Luberoff, 1969). 

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