In the realm of cross-couplings that involve a single functionalized reaction partner, key contributions have come from many investigators across a range of reactions and catalyst types (Scheme 1A). As representatives examples, contributions from Doyle and MacMillan disclosed metallaphotoredox-catalyzed C-H arylations, where the C(sp 3 )-H bonds in dimethylaniline were converted into organic radicals that undergo cross-couplings with aryl halides. The Doyle group has further developed the direct functionalization of C(sp 3 )-H bonds of N-aryl amines by acyl electrophiles under metallaphotoredox conditions. Following these reports, the fields of photoredox catalysis and hydrogen atom transfer (HAT) have experienced rapid growth with broad scope being demonstrated in a-amino C(sp )-H functionalization with different coupling partners, including halides, 7 activated acids, 8 acrylates 9 , azoliums, 10 amides. Of these and related reports, work from Doyle, Scheidt, Hong, Huo, Xu, Ohmiya, and Chi 14 describe acylation processes using an array of electrophile classes. Among various HAT agents explored, peroxide oxidants have been demonstrated by Lei as effective in nickel-catalyzed C-H activation processes of heterocyclic C(sp 3 )-H bonds. Recent work from Stahl illustrating C-H methylation processes via cross-selective radical-radical couplings relying on methyl radical extrusion and from Gong demonstrating the co-utilization of a peroxide oxidant with a zinc reductant provide important examples of peroxide-mediated processes with nickel involving free radicals generated by HAT processes.