Electrochemical [2+2+1] Dimerization Annulation of Styrenes and TMSN₃ via Schmidt Rearrangement: Direct Access to 1-Pyrrolines

A significant advancement has been made in the dimerization and cyclization of styrenes in one step to construct nitrogen-containing heterocyclic skeletons. Herein, we report a novel [2+2+1] dimerization annulation of styrenes and TMSN₃ via Schmidt rearrangement, enabling straightforward access to 1-pyrrolines from the most easily available materials. Different from 5-<i>exo</i>-trig cyclization, this strategy not only obviated the needs of an oxidant, a metal, and presynthesis but also possessed simple and green operations. Besides, mechanistic studies indicated a radical pathway was involved, which was further demonstrated by DFT computational analysis. These findings highlight the potential of direct electro-activation of olefins to address the existing challenges in dimerization cyclization of olefins.