Palladium‐Catalyzed Thiomethylation of Arenes: A Convenient Method for Molecular Electronics Applications

Thiomethyl groups (─SMe) are highly relevant in molecular electronics, particularly in studies exploring single‐molecule electron transport using the scanning tunneling microscope‐break junction (STM‐BJ) technique. These groups play a crucial role by acting as anchoring groups for gold electrodes. However, general synthetic methodologies for installing this functional group are scarce. Herein, we present a palladium‐catalyzed reaction for the thiomethylation of aryl iodides, bromides, and triflates using NaSMe as the nucleophilic reagent. This methodology is robust, scalable, and exhibits broad functional group compatibility and structural diversity.