Ligand‐Free Transition‐Metal‐Catalyzed Suzuki–Miyaura Cross‐Coupling: Advances in Homogeneous and Heterogeneous Catalysis (2016–2025)

The Suzuki–Miyaura cross‐coupling reaction between organohalides and organoboron compounds is one of the most powerful methods for the synthesis of biaryl frameworks. Many biologically and industrially important molecules, including pharmaceuticals, natural products, chiral ligands, and catalysts, feature biaryl scaffolds that are crucial to their properties and functions. Ongoing research continues to expand the scope of ligand‐free transition‐metal catalysis, underscoring its significance in modern synthetic organic chemistry. The absence of ligands not only simplifies reaction protocols but also reduces costs and chemical waste. This review highlights both seminal early studies and recent advances in ligand‐free Suzuki–Miyaura cross‐coupling catalyzed by palladium and other transition‐metals such as copper, ruthenium, rhodium, silver, and gold over the past decade.