Iron-Catalyzed CαH Oxidation of Tertiary, Aliphatic Amines to Amides under Mild Conditions

De novo syntheses of amides often generate stoichiometric amounts of waste. Thus, recent progress in the field has focused on precious metal catalyzed, oxidative protocols to generate such functionalities. However, simple tertiary alkyl amines cannot be used as starting materials in these protocols. The research described herein enables the oxidative synthesis of amides from simple, noncyclic tertiary alkyl amines under synthetically useful, mild conditions through a biologically inspired approach: Fe‐catalyzed CαH functionalization. Mechanistic investigations provide insight into reaction intermediates and allow the development of a mild CαH cyanation method using the same catalyst system. The protocol was further applied to oxidize the drug Lidocaine, demonstrating the potential utility of the developed chemistry for metabolite synthesis. Eisern, aber milde: Die Titelreaktion ermöglicht die oxidative Synthese von Amiden direkt aus tertiären, nichtcyclischen Alkylaminen unter präparativ nützlichen milden Bedingungen nach einem biologisch inspirierten Ansatz unter Verwendung oxidativer Eisenkatalyse. Mechanistischen Studien zufolge sind Halbaminale wahrscheinliche Intermediate dieser Reaktion. Mit diesem System könnten sich auch andere Cα‐H‐Oxidationen von Aminen verwirklichen lassen.