Electrolysis-Assisted Reduction of Dimethylformamide for Unactivated Alkene Functionalizations

<i>N,N</i>-Dimethylformamide is a widely used solvent, which can be employed as a reagent under certain conditions. Among the different ionic and radical activation approaches, the direct single-electron reduction of this amide appears elusive, owing to its prohibitively low reductive potential. In this work, electrolysis-assisted generation of the <i>N,N</i>-dimethylformamide distonic radical anion is presented. Its synthetic applicability was established by the functionalization of unactivated alkenes. The transformation was validated across several mono- and disubstituted olefins, generating the corresponding hydroformylated and hydroaminomethylated products. Mechanistic experiments confirmed the generation of the distonic radical, demonstrating that this intermediate was generated at the surface of the magnesium anode. This work provides a new perspective on the activation of this commonly used solvent, paving the way to other radical transformations.