Owing to their non‐toxic, stable, inexpensive properties, carboxylic acids are considered as environmentally benign alternatives as coupling partners in various organic transformations. Electrochemical mediated decarboxylation of carboxylic acid has emerged as a new and efficient methodology for the construction of carbon‐carbon or carbon‐heteroatom bonds. Compared with transition‐metal catalysis and photoredox catalysis, electro‐organic decarboxylative transformations are considered as a green and sustainable protocol due to the absence of chemical oxidants and strong bases. Further, it exhibits good tolerance with various functional groups. In this Minireview, we summarize the recent advances and discoveries on the electrochemical decarboxylative transformations on C−C and C−heteroatoms bond formations.

Decarboxylative C sp 3 −N coupling reactions have been developed through electrochemical oxidation of amino acids. The reaction proceeds via anodic oxidative decarboxylation of carboxylic acids to form stabilized carbocations, which are trapped by azoles or amides to construct C−N bonds. This method avoids the preactivation of carboxylic acids and the use of expensive transition-metals and external chemical oxidants.

The nucleophilic substitution reactions of hydroxyl groups are one of the most fundamental and widely-spread transformations in organic chemistry. Among them, PIII-mediated deoxygenative nucleophilic substitution reactions, such as Mitsunobu reaction,...