Metal-catalyzed CH activation/functionalization: The fundamentals

•The fundamentals of transition metal catalyzed CH bond activation are described.•Mechanistic studies of the CH bond activation/functionalization reactions are presented.•Pioneering works and major breakthroughs are illustrated.

An isolated CH bond in a molecule has a very low reactivity owing to the large kinetic barrier associated to the CH bond cleavage and the apolar nature of this bond. For this reason, the selective reactivity of such a non-functional group is under active study since several decades and is still regarded as the Holy Grail in chemistry. Metal-catalyzed CH activation/functionalization chemistry allows the step-economical and original construction of CC as well as CO and CN bonds starting from hydrocarbons (or hydrocarbon fragments) without the need of prior non catalytic oxidation steps. Furthermore, it can be of utmost importance in the domain of multistep syntheses, and also in transformations of societal significance such as the conversion of methane into methanol. This tutorial review addresses to students and researchers who would like to become acquainted with this fascinating topic. After a brief historical introduction, the main mechanistic fundaments of metal-catalyzed CH activation are exposed. Then, a selection of seminal advances and conceptual breakthroughs are presented.

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