Forging Amide Bonds via Metal‐Catalyzed Cross‐Coupling Reactions with Isocyanates

The natural occurrence of amides and their unique role in synthetic materials and biologically active molecules makes amide synthesis one of the most routinely performed reactions in organic chemistry. Despite the advances realized, there is a growing need for designing new catalytic technologies that complement existing amide bond‐forming reactions, which often rely on the formation of the carbon‐nitrogen bonds. The recent years have witnessed the design of a new disconnection approach to forge amide bonds by means of metal‐catalyzed carbon‐carbon bond‐forming reactions. This microreview highlights the most recent developments on the use of isocyanates in metal‐catalyzed amidations that occur via this design principle. With the aim of illustrating the prospective impact of the use of isocyanates as amide synthons, this account will highlight the advantages and drawbacks of the existing methods, and describe the mechanistic implications, when appropriate.