A Ni–Ir Dual Photocatalytic Liebeskind Coupling of Sulfonium Salts for the Synthesis of 2‐Benzylpyrrolidines

A new method has been developed for the synthesis of 2‐benzylpyrrolidines utilizing cross‐coupling and photoredox catalysis. Using a well‐established dual Ni–Ir system, we were able to successfully couple benzylsulfonium salts with proline utilizing radical forming through CO 2 extrusion. This enabled the simple one‐step synthesis of 2‐benzylpyrrolidines from stable, inexpensive starting materials.