Iron‐catalyzed CH activation has attracted great interest over the past couple of decades as a promising technique to establish CC bond‐forming functionalities for complex molecule design. The motivation behind this trend can be attributed to the low cost, minimal toxicity, and rich oxidation chemistry afforded by iron. The synthetic utility of iron catalysis for CH activation/functionalization was widely recognized following the development of an iron‐catalyzed CH activation system that facilitated the cross‐coupling of a CH bond with an organometallic reagent under oxidative conditions. Following this seminal approach, iron‐catalyzed CH activation has been widely explored to establish CC bonds across a variety of functionalities. This article underscores the evolution of CC bond‐forming iron‐catalyzed CH activation by providing several examples across a broad range of CH functionalizations including alkylation, alkenylation, alkynylation, allylation, arylation, and annulation that involve CH‐activated organoiron species through the reaction of a substrate CH bond with an iron catalyst. An additional section of this article is dedicated to highlighting the key mechanistic insights into iron‐catalyzed CH functionalization, a field that is largely underdeveloped yet invaluable toward the rational development of the next generation of systems in iron‐catalyzed CH activation/functionalization.
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