Dual C2 Synthon Strategy for the Synthesis of Pyrimidines: Copper‐Catalyzed Aerobic α,β‐C(sp3)‐H Bond Difunctionalization of Tertiary Alkylamines

Herein, we describe a two‐component methodology developed for the synthesis of pyrimidine derivatives using tertiary alkylamines and amidines. Tertiary alkylamines serve as dual C2 synthons through copper‐catalyzed aerobic difunctionalization of the α,β‐C(sp3)‐H bonds. The process operates under mild conditions and uses atmospheric oxygen as the oxidant. Notably, this methodology yields up to 85% and shows a broad substrate scope. Mechanistic studies indicate that the annulation proceeds via a radical‐mediated oxidation and C‒N bond coupling process. This approach provides a pathway for synthesizing various heterocycles by employing tertiary alkylamines as dual C2 synthons.