Organic halides to form esters and amides

Carbonylations of Organic Halides to form Esters and Amides 

The first palladium-catalyzed carbonylations of aryl halides were published in 1974 and 1975 (Equation 17.59). ° Heck first reported the synthesis of benzoates by the reaction of an aryl iodide, carbon monoxide, and an alcohol in the presence of a tertiary amine and catalytic amoimts of the combination of palladium acetate and triphenylphosphine. Concurrently, he reported the synthesis of benzamides from an aryl iodide, carbon monoxide, a primary amine, and a tertiary amine as base catalyzed by the same type of palladium complex. The related reactions of vinyl halides were also reported, and these reactions occurred with retention of the olefin geometry.  

More recently, Osbom and Milstein reported the reactions of aryl chlorides with carbon monoxide and a base to form aromatic esters, and Alper reported related reactions of aryl chlorides in biphasic media to form carboxylic acids. The reaction of Milstein is shown in Equation 17.60, and the reactions of Osborn were conducted imder similar conditions with PCyj as ligand. These examples comprise some of the first coupling chemistry performed with aryl chlorides. 

The carbonylations of haloarenes have also been conducted intramolecularly. Examples of these reactions to form lactams.are represented genetically in Equation 17.6P along with specific examples to form benzolactams. The carbonylations of haloarenes has also been applied to the synthesis of polymers. As shown in Equation 17.62, these reactions can be conducted between dihaloarenes and diamines to form polyaramide materials.  

In addition to the carbonylation of aryl and vinyl halides, the carbonylation of aryl and vinyl ttiflates to form esters and amides has been conducted. An example of these reactions is shown in Equation 17.63.  

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See also in sourсe #XX -- [ , , ]

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