Stereodivergent synthesis of chiral amines bearing vicinal stereocenters via hydroamination of trisubstituted alkenes.

Chiral aliphatic amines bearing vicinal stereocenters are prevalent motifs in pharmaceuticals and bioactive molecules, yet efficient and stereodivergent access to these structures remains a longstanding challenge. Herein, we report a nickel-catalyzed enantioselective hydroamination of acyclic trisubstituted alkenes that provides a unified platform for the stereodivergent construction of chiral amines bearing β,γ-stereocenters. The reaction exhibits broad substrate scope, accommodating diverse amine electrophiles and tri-substituted alkenes, including those derived from complex bioactive molecules, with high levels of regio-, diastereo-, and enantioselectivity. By modulating the alkene geometry and the configuration of a chiral biimidazoline ligand, all four stereoisomers can be accessed in a predictable manner. The protocol proceeds under mild conditions, tolerates various functional groups, and enables late-stage derivatization, demonstrating its utility for constructing densely functionalized, three-dimensional amine scaffolds. This work provides a valuable platform for asymmetric synthesis and holds strong potential for drug discovery and molecular design.