Cobalt-Catalyzed Migratory E-Selective Asymmetric Aza-Nozaki-Hiyama-Kishi Coupling.

Transition-metal-catalyzed migratory cross-coupling offers an attractive strategy for converting readily available precursors into complex molecular architectures. However, current methods are typically restricted to a single migratory mode (e.g., chain-walking, through-space shift, or E/Z isomerization). Integrating multiple mechanistically distinct migratory events within a selective cross-coupling manifold to unlock new chemical space and diverse isomeric products remains a formidable challenge. Herein, we report a cobalt-catalyzed, migratory E-selective asymmetric aza-NHK (Nozaki-Hiyama-Kishi) coupling of ortho-iodophenylethylenes with imines. The key to this process is a synergistic sequence that combines a through-space 1,4-Co/H shift with alkenylcobalt E/Z isomerization. Notably, mixtures of E/Z-alkenyl bromides are also viable substrates, undergoing an unprecedented alkenylcobalt E/Z isomerization prior to E-selective asymmetric coupling. This method provides efficient access to high-value α-chiral (E)-allylic amines with exceptional control over regio-, E/Z-, and enantioselectivity.