Manganese-Catalyzed C–H Activation

Manganese is found in the active center of numerous enzymes that operate by an outer-sphere homolytic C–H cleavage. Thus, a plethora of bioinspired radical-based C–H functionalizations by manganese catalysis have been devised during the past decades. In contrast, organometallic C–H activation by means of manganese catalysis has emerged only recently as an increasingly viable tool in organic synthesis. These manganese(I)-catalyzed processes enabled a variety of C–H functionalizations with ample scope, which very recently set the stage for substitutive C–H functionalizations. The versatile manganese catalysis largely operates by an isohypsic, thus redox-neutral, mode of action through chelation assistance, and provided step-economical access to structurally divers compounds of relevance to inter alia bioorganic, agrochemical, and medicinal chemistry as well as the material sciences.