Diradical Polar Reactivity Induced by Electricity‐Mediated Ground State Triplet Nitrenium Species

It is extremely rare for reactive intermediates to possess a ground state triplet character. Excited state triplet intermediates are generally accessed by means of photon transfer from a tunable light source or by using any triplet sensitizers. N ‐acyl N ‐alkoxy nitreniums are an important class of reactive intermediates in the synthetic organic community due to their prolonged lifetime and ground‐state singlet character. Herein, we report an external oxidant and toxic catalyst‐free mild electrochemical protocol to access nitrenium reactive intermediate. Experimental findings of the mechanistic pathway suggested a theoretically predicted triplet reactive intermediate that is energetically favorable compared to the singlet pathway.