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

Abstract 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( sp 3 )−H bonds. The process operates under mild conditions and uses atmospheric oxygen as the oxidant. Notably, by this methodology yields up to 85% yields are obtained and a broad substrate scope is shown. 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.