Electrochemical and Photoelectrochemical Transformations of Thioamides

Abstract Pursuing innovative and environmentally friendly synthetic strategies is always a desirable goal in organic synthesis, and thus, we have developed green and sustainable electrochemical (EC) and photoelectrochemical ( i PEC) transformations of thioamides into amides. The established EC protocol is inexpensive, mild, and metal‐ and catalyst‐free. i PEC cells are extensively studied for solar energy conversion, but their application in synthesizing high‐value organic molecules has been limited. Here, we describe a strategy to use BiVO 4 , an abundant and robust photoanode, for the desulfurization of thioamides. Under light irradiation, the photogenerated holes in BiVO 4 oxidize thioamides to radical cations, which further react with the oxygen radical anion to produce amides. The proposed i PEC strategy presents a high promise for green organic chemical transformations with the goal of maximizing not only the atom economy but also the energy efficiency.