Nickel-Catalyzed Aminoxylation of Inert Aliphatic C(sp<sup>3</sup>)–H Bonds with Stable Nitroxyl Radicals under Air: One-Pot Route to α‑Formyl Acid Derivatives

Nickel-catalyzed aminoxylation of an unactivated C­(sp<sup>3</sup>)–H bond with a stable nitroxyl radical has been accomplished for the first time to offer various <i>N</i>-alkoxyamine derivatives, which further enables a one-pot approach to α-formyl acid derivatives. The aminoxylation process reported also provides direct evidence for the oxidative addition of a cyclometallic intermediate with a free radical, which is helpful for the reaction-mechanism study in transition-metal-catalyzed functionalization of inert C­(sp<sup>3</sup>)–H bonds.