Skeletal Editing of (Hetero)Arenes Using Carbenes

(Hetero)arenes continue to prove their indispensability in pharmaceuticals, materials science, and synthetic chemistry. As such, the controllable modification of biologically significant (hetero)arenes towards diverse more‐potent complex molecular scaffolds through peripheral and skeletal editing has been considered a challenging goal in synthetic organic chemistry. Despite many excellent reviews on peripheral editing (i. e., C−H functionalization) of (hetero)arenes, their skeletal editings via single atom insertion, deletion, or transmutations have received less attention in the review literature. In this review, we systematically summarize the state‐of‐the‐art skeletal editing reactions of (hetero)arenes using carbenes, with a focus on general mechanistic considerations and their applications in natural product syntheses. The potential opportunities and inherent challenges encountered while developing these strategies are also highlighted. This review summarizes the state‐of‐the‐art developments in the skeletal editing of (hetero)arenes using carbenes, with an emphasis on the scope, reactivity, selectivity, and general mechanistic considerations. The impressive breadth of application of this strategy in both drug discovery and total synthesis is also discussed. Existing challenges and perspectives on future research directions to further understanding and new reaction developments are outlined.