Methods that utilize cross dehydrogenative couplings (CDCs) through C-H functionalization on two different unfunctionalized reaction partners are highly desirable but quite rare. Extensive work from Li has examined cross hydrogenative couplings using copper catalysis (Scheme 1B), while fundamental studies from Fagnou illustrated biaryl synthesis through palladium-catalyzed cross-couplings of two arenes with cross selectivity arising from electronic differences in the two arene substrates. C-H activations in CDCs typically operate via different modes, with one of the two substrates bearing acidic protons that enables the formation of a reactive species through acid-base chemistry, while the other substrate undergoes HAT-mediated C-H cleavage. 21 Scheme 1. Strategies in C(sp 3 )-H functionalization Based on the above advances, we envisioned that the versatile chemistry of nickel in mediating radical-based cross-coupling processes could potentially be paired with HAT chemistry to enable C-H activation methods on two different substrates, thus avoiding functional groups preinstallation. A strategy of this type could potentially allow two different C-H activation processes to simultaneously operate even when the two substrates possess C-H bonds that are not easily distinguished by acidity or bond strength. Towards the goal of developing a nickel-catalyzed direct oxidative dehydrogenative coupling process, we set out to examine the coupling of aldehydes with N-heterocycles (Scheme 1C), with these studies being motivated by our longstanding interest in the development of nickel-catalyzed additions to aldehydes utilizing unconventional nucleophiles. Herein, we describe the formation of unsymmetrical ketones through the direct acylation of a-amino C(sp 3 )-H bonds with aldehydes in a nickel-catalyzed process utilizing peroxide oxidant as the source of the HAT agent.