New Approaches to the Synthesis of Metal Carbenes

Abstract Metal carbenes usually possess versatile reactivities that are controlled by the presence of both the metals and the ligands. Diazo compounds are commonly used for the generation of such species through elimination of nitrogen. However, they are often unstable, explosive, and toxic, which limits their applications in large‐scale syntheses. Thus, identifying sustainable and safe surrogates for the generation of metal carbenes has attracted great attention. In this Review, we summarize some of the most important breakthroughs in the generation, catalytic reactions, and selectivity control of metal carbenes from non‐diazo starting compounds.