Metalla-electrocatalyzed C-H Activation by Earth-Abundant 3d Metals and Beyond.

To improve the efficacy of molecular syntheses, researchers wish to capitalize upon the selective modification of otherwise inert C-H bonds. The past two decades have witnessed considerable advances in coordination chemistry that have set the stage for transformative tools for C-H functionalizations. Particularly, oxidative C-H/C-H and C-H/Het-H transformations have gained major attention because they avoid all elements of substrate prefunctionalization. Despite considerable advances, oxidative C-H activations have been dominated by precious transition metal catalysts based on palladium, ruthenium, iridium, and rhodium, thus compromising the sustainable nature of the overall C-H activation approach. The same holds true for the predominant use of stoichiometric chemical oxidants for the regeneration of the active catalyst, prominently featuring hypervalent iodine(III), copper(II), and silver(I) oxidants. Thereby, stoichiometric quantities of undesired byproducts are generated, which are preventive for applications of C-H activation on scale. In contrast, the elegant merger of homogeneous metal-catalyzed C-H activation with molecular electrosynthesis bears the unique power to achieve outstanding levels of oxidant and resource economy. Thus, in contrast to classical electrosyntheses by substrate control, metalla-electrocatalysis holds huge and largely untapped potential for oxidative C-H activations with unmet site selectivities by means of catalyst control. While indirect electrolysis using precious palladium complexes has been realized, less toxic and less expensive base metal catalysts feature distinct beneficial assets toward sustainable resource economy. In this Account, I summarize the emergence of electrocatalyzed C-H activation by earth-abundant 3d base metals and beyond, with a topical focus on contributions from our laboratories through November 2019. Thus, cobalt electrocatalysis was identified as a particularly powerful platform for a wealth of C-H transformations, including C-H oxygenations and C-H nitrogenations as well as C-H activations with alkynes, alkenes, allenes, isocyanides, and carbon monoxide, among others. As complementary tools, catalysts based on nickel, copper, and very recently iron have been devised for metalla-electrocatalyzed C-H activations. Key to success were detailed mechanistic insights, prominently featuring oxidation-induced reductive elimination scenarios. Likewise, the development of methods that make use of weak O-coordination benefited from crucial insights into the catalyst's modes of action by experiment, in operando spectroscopy, and computation. Overall, metalla-electrocatalyzed C-H activations have thereby set the stage for molecular syntheses with unique levels of resource economy. These electrooxidative C-H transformations overall avoid the use of chemical oxidants and are frequently characterized by improved chemoselectivities. Hence, the ability to dial in the redox potential at the minimum level required for the desired transformation renders electrocatalysis an ideal platform for the functionalization of structurally complex molecules with sensitive functional groups. This strategy was, inter alia, successfully applied to scale-up by continuous flow and the step-economical assembly of polycyclic aromatic hydrocarbons.