Reduced Copper-catalyzed Conversion of a Mixture of Primary Alcohols and Secondary Alcohols into Esters and Ketones

Abstract

The reduced copper-catalyzed reactions between a secondary alcohol containing m carbon atoms and a primary alcohol or aldehyde containing n carbon atoms were performed under various conditions to clarify the mechanism of the formation of esters in this reaction. The catalyzed reactions resulted in the formation of esters containing md-n carbon atoms and ketones containing m, 2 m, 3 m, m+n, and 2 n-1 carbon atoms. It was proved that the esters were produced via a hemiacetal intermediate which was formed from the secondary alcohol and the aldehyde. On the other hand, it was found that the ketones containing 2 m, 3 m, and m-Fn carbon atoms were formed by condensation between the ketone produced from the secondary alcohol and the starting alcohol, and the ketone containing 2 n-1 carbon atoms was formed by elimination of carbon monoxide and hydrogen from the hemiacetal intermediate produced from the primary alcohol and the corresponding aldehyde.