Deoxygenative Allylation of Amides/Aldehydes via Interconvertible Intermediates: Switchable Access to α- or β-Allylated Alkylamines

The efficient and selective synthesis of alkylamines is critically important for organic chemistry and drug discovery. Nevertheless, developing catalytic protocols that allow for switchable access to structurally diverse alkylamines from readily available precursors remains a significant challenge. While deoxygenation of amides/aldehydes offers efficient alkylamine synthesis, prior methods are largely confined to α-substituted products, limiting structural diversity. Herein, we report a strategy that overcomes this key limitation, enabling regiodivergent access to either α- or β-allylated alkylamines with high selectivity. Starting from abundant amides and allylic halides, utilization of the in situ formed iminium or enamine intermediate dictates switchable regio-chemistry to provide a versatile platform for the synthesis of complex amines. Furthermore, a tandem Ni–Ir catalytic system achieves a one-step β-allylated amine synthesis via three-component coupling of aldehydes, amines, and allylic halides, bypassing traditional α-selectivity. This methodology delivers switchable regiocontrol and broad scope from readily available starting materials, significantly expanding synthetic access to valuable alkylamine building blocks.