Single‐Atom Skeletal Editing of Aromatics: Advances in Carbon‐to‐Nitrogen and Nitrogen‐to‐Carbon Transmutation

The selective modification of aromatic ring systems through single‐atom skeletal editing has emerged as a transformative strategy in modern organic synthesis. Among the most compelling advances are carbon‐to‐nitrogen (C‐to‐N) and nitrogen‐to‐carbon (N‐to‐C) transmutations, which enable precise atomic substitutions within heteroaromatic frameworks without disrupting the surrounding molecular architecture. This review comprehensively summarizes recent developments in these two complementary transformations, highlighting both mechanistic innovations and synthetic applications. C‐to‐N transmutation strategies, including oxidative ring expansion and electrophilic rearrangement, have enabled the conversion of quinolines and related azaarenes into pharmaceutically relevant quinazolines. Conversely, N‐to‐C editing approaches such as ring‐opening, skeletal rearrangement, and rearomatization allow the deconstruction of nitrogen‐containing heterocycles like pyridines into substituted benzenes. These methodologies have opened new avenues in drug design, late‐stage functionalization, and heterocycle diversification. The review also discusses the current limitations, mechanistic insights, and future opportunities for extending single atom editing to broader classes of aromatic systems, positioning this field at the forefront of molecular editing and precision synthesis.