Transition‐Metal‐Catalyzed CH Activation Assisted by N,O‐Bidentate Directing Groups

During the past decades, transition‐metal‐catalyzed CH functionalization has gained recognition as a powerful method in organic synthesis. This strategy provides efficient and atom‐economical pathways for quickly creating molecular complexity by harnessing the abundant CH bonds found in readily accessible chemical feedstocks. Synthetic organic chemists discover directing group (DG)‐assisted CH activation as a key tool for achieving efficient and site‐selective CH functionalization. Bidentate directing groups are particularly effective in this regard, offering a high degree of control over the reaction site. Among various directing groups, N,O ‐bidentate systems have gained significant attention due to their strong coordinating ability and versatility in enabling regioselective transformations. This review highlights recent advances in CO, CN, CS, CB, and CC bond formation reactions facilitated by N,O ‐bidentate directing groups. The discussion encompasses mechanistic insights, catalyst systems, and synthetic applications, demonstrating the broad utility of these strategies in modern organic synthesis. A comparative analysis of different N,O ‐bidentate ligands and their role in tuning reactivity and selectivity is also presented.