Abstract
AbstractC(sp3)−H functionalization methods have been widely employed in many organic transformations such as cyclization reactions, heterocycle synthesis, cross‐coupling protocols, and photochemical transformations. Among these transformations, cyclization reaction through C(sp3)−H functionalization offers a direct route to convert simple linear substrates to complex products. There are three common modes of utilizing C(sp3)−H bonds in cyclization reactions including single, double, and dual C(sp3)−H functionalization. As the most challenging mode, dual C(sp3)−H functionalization refers to converting two separate C(sp3)−H bonds in one molecule into desired C−Z bonds which can be employed in cyclization reactions. Cyclization reaction via dual functionalization of C(sp3)−H bonds can be classified based on the C−H reactivities. Therefore, these reactions can be categorized into three classes based on the types of C(sp3)−H bonds including activated‐activated, activated‐unactivated, and unactivated‐unactivated C(sp3)−H bonds. Most published reports for cyclization reactions through dual C(sp3)−H functionalization involve activated‐activated C(sp3)−H bonds. However, the number of reported papers on the other two classes has been growing. This review focuses on the dual C(sp3)−H functionalization protocols used for cyclization reactions and categorizes the published papers based on the types of C(sp3)−H bonds.
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