Electrophotocatalytic decarboxylative vicinal dichlorination of aliphatic carboxylic acids

Abstract

Decarboxylative functionalization of aliphatic carboxylic acids is a powerful strategy in organic synthesis, yet most methods focus on decarboxylative monofunctionalization. Merging decarboxylation with selective activation of an adjacent C–H bond to deliver vicinal difunctionalization has remained elusive. Here we report an electrophotocatalytic decarboxylative vicinal dichlorination of aliphatic carboxylic acids using 1,2-dichloroethane as both the solvent and the chlorine source. Mechanistic studies indicate the formation of an alkene intermediate via photocatalytic dehydrogenative decarboxyolefination, followed by electrochemical vicinal chlorination. The protocol operates under mild conditions, tolerates diverse functionality and enables late-stage vicinal dichlorination of bioactive molecules and natural products, underscoring its practicality and potential for streamlined synthesis. Decarboxylative functionalization of aliphatic carboxylic acids is a powerful strategy in organic synthesis, yet most methods focus on decarboxylative monofunctionalization. Now, an electrophotocatalytic decarboxylative vicinal dichlorination of aliphatic carboxylic acids has been developed to enable late-stage decarboxylative difunctionalization of bioactive molecules and natural products.