Carboxylic acids unimolecular cleavage

For example, in the case of protonated carboxylic acids in HS03F-SbF5-S02 solution, a reaction analogous to the rate-determining step in the unimolecular cleavage of esters is observed leading to the acyl cation and oxonium (hydronium) ion [Eq. (3.67)]. 

By raising the temperature of solutions of protonated carboxylic acids and esters, unimolecular cleavage reactions are observed. These reactions can be considered within the framework of the two unimolecular reaction pathways for acid-... 

A typical example of the microdielectric catalysis by cyclodextrins is the decarboxylation of anions of activated acids such as a-cyano and y8-keto acids [15]. These reactions proceed unimolecularly via rate-determining heterolytic cleavage of the carbon-carbon bond adjacent to the carboxylate group (Scheme 3). 

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