Abstract
A protocol for the aminomethylation of aryl halides using α-silylamines via Ni/photoredox dual catalysis is described. The low oxidation potential of these silylated species enables facile single electron transfer (SET) oxidation of the amine followed by rapid desilylation. The resulting α-amino radicals can be directly funneled into a nickel-mediated cross-coupling cycle with aryl halides. The process accomplishes aminomethylation under remarkably mild conditions and tolerates numerous aryl- and heteroaryl halides with an array of functional groups.