Ternary Aldehyde‐Copper‐Iridium Catalysis Enables Stereodivergent Allylation via α‐C‐H Functionalization of Primary Amines

α‐Chiral primary amines are recognized as one of the most valuable and versatile synthetic intermediates, widely utilized in the construction of diverse amine‐containing natural products, pharmaceuticals, and agrochemicals. The direct asymmetric α‐C‐H functionalization of unprotected primary amines is the most straightforward method for creating these motifs. However, this transformation remains underdeveloped, particularly in stereodivergent synthesis of primary amines with multiple stereocenters. Herein, we report an aldehyde/copper/iridium ternary catalytic system, which was successfully employed for the direct enantio‐ and diastereodivergent α‐allylation of primary α‐amino‐chromanone without requiring additional protection or activation of the NH2 group. A wide range of α‐tertiary primary amines bearing vicinal stereocenters were prepared in high yields with excellent enantio‐ and diastereoselectivities (generally >20:1 dr and >99% ee). Notably, all four stereoisomers of the α‐tertiary amines can be readily prepared by simply switching the configuration combinations of the two chiral metal catalysts. Furthermore, the asymmetric induction model for the α‐C‐H functionalization of primary amines was meticulously elucidated through comprehensive density functional theory (DFT) calculations.