Skeletal Editing of 6‐(Hetero)arenes via Single‐Carbon‐Atom Insertion

Abstract The skeleton editing strategy has emerged as a transformative approach in drug discovery and agrochemical innovation, enabling precise modifications through the insertion, elimination, or substitution of specific atoms within the core carbon‐ or heterocyclic frameworks of molecules. Recent advancements in carbene chemistry have led to significant breakthroughs in single‐carbon‐atom insertion reactions, particularly in the context of five‐membered carbon‐ and heterocyclic systems. However, the application of this strategy to six‐membered arenes and heteroarenes has faced considerable challenges, largely due to the thermodynamic and kinetic barriers associated with disrupting the inherent aromaticity of these systems and driving their conversion to seven‐membered rings. In recent years, the development of novel catalytic paradigms, including photo‐ and electro‐catalytic methods, has catalyzed groundbreaking progress in this area. Notably, the design and implementation of asymmetric skeletal editing systems for arenes have significantly expanded the scope and versatility of this methodology, offering new avenues for the rational manipulation of molecular architectures. This review aims to offer a detailed summary and analysis of recent progress in skeletal editing reactions associated with single‐carbon‐atom insertion and outlining the future potential applications of this technology.