Metal‐Catalyzed Dehydration of Primary Amides to Nitriles

Abstract The dehydration of primary amides to generate their respective nitriles is an isohypsic, or redox neutral, method to install a valuable functional group into a molecule. This process has been known for over 175 years, typically using highly reactive dehydrating agents and high temperatures. Recently, transition metal‐catalysis has enabled reactivity under milder reaction conditions, while also tolerating a wide range of functional groups. The removal of water from primary amides is still energetically uphill so a stoichiometric dehydrating agent is required. The dehydrating agents used in recent years can be rather benign, such as acetonitrile to generate acetamide. This Minireview focuses on metal‐catalyzed reactions to convert primary amides into nitriles and is organized based on the dehydrating agent.