Evolution of High-Valent Nickela-Electrocatalyzed C-H Activation: From Cross(-Electrophile)-Couplings to Electrooxidative C-H Transformations

C-H activation has emerged as one of the most efficient tools for the formation of carbon-carbon and carbon-heteroatom bonds, avoiding the use of prefunctionalized materials. In spite of tremendous progress in the field, stoichiometric quantities of toxic and/or costly chemical redox reagents, such as silver(I) or copper(II) salts, are largely required for oxidative C-H activations. Recently, electrosynthesis has experienced a remarkable renaissance that enables the use of storable, safe and waste-free electric current as a redox equivalent. While major recent momentum was gained in electrocatalyzed C-H activations by 4d and 5d metals, user-friendly and inexpensive nickela-electrocatalysis has until recently proven elusive for oxidative C-H activations. Herein, the early developments of nickela-electrocatalyzed reductive cross-electrophile couplings as well as net-redox-neutral cross-couplings are first introduced. The focus of this Minireview is, however, the recent emergence of nickel-catalyzed electrooxidative C-H activations until April 2020.