Electrochemical conversion of carboxylic acids to terminal alkenes enabled by dialkyl phosphate electrolyte

Electrochemical regioselective conversion of carboxylic acids to terminal alkenes through dehydrogenative decarboxylation was developed. Mechanistic studies suggested that the reaction proceeds through oxidative decarboxylation of carboxylic acids to give the corresponding primary carbocation intermediates followed by deprotonation. It was implied that when using a supporting electrolyte with high donor number anion, such as dialkyl phosphate, the isomerization of the primary carbocation intermediates was suppressed to cause higher selectivity to terminal alkenes. • Electrochemical conversion of carboxylic acids to terminal alkenes with high selectivity is achieved. • Using tetramethylammonium dibutyl phosphate as the supporting electrolyte enabled the high selectivity. • The supporting electrolyte can stabilize the highly active primary carbocation intermediate.