Recent Advances in Ru‐Catalyzed CH Bond Functionalization for CC Bond Construction

Strategic activation of inert CH bonds is a cornerstone of modern organic synthesis, offering atom‐economical pathways for constructing complex molecules. Within this critical domain, ruthenium catalysts have emerged as exceptionally powerful and versatile tools, distinguished by their unique reactivity, selectivity, and stability. This review comprehensively summarizes the latest advancements over the past 5 years in Ru‐catalyzed CH bond functionalization for CC bond construction, encompassing arylation, alkenylation, alkylation, and cyclization reactions. It highlights significant breakthroughs in achieving precise control, including challenging remote C–H activation. Central to these achievements is a deepened mechanistic understanding, particularly concerning the crucial role of bicyclic metallacycle intermediates and the growing adoption of photoredox radical pathways. Moreover, the paper showcases innovative green methodologies such as mechanochemistry and photocatalysis, reflecting a strong drive toward more sustainable synthetic practices. Collectively, these developments underscore the immense potential of ruthenium catalysis in building intricate molecular architectures, securing its indispensable position in contemporary synthetic chemistry.