Recent Advances in Direct C–H Functionalization of Unprotected Anilines via Catalytic and Metal‐Free Strategies

Anilines constitute a central structural motif in a wide range of pharmaceuticals and functional materials; however, their direct C–H functionalization has long been constrained by preferential N ‐reactivity and limited control over regioselectivity. Recent advances have transformed this landscape by enabling highly selective ortho ‐ and para ‐C–H functionalization of unprotected anilines through diverse catalytic and metal‐free strategies. This review highlights key breakthroughs in C–C and C–heteroatom bond formation, mechanistic control of selectivity, and late‐stage functionalization of complex molecules. The literature covered spans the period from 2020 to 2025, offering a timely and critical perspective on emerging trends and future opportunities.