Nickel(0)‐Catalyzed Enantioselective Three‐Component Imino–Ene‐Type Coupling of Aldehydes, Sulfonamides, and Alkenes

ABSTRACT Enantioenriched homoallylic amines are common motifs in bioactive molecules and versatile intermediates in nitrogen‐containing molecule synthesis. We report a Ni(0)‐catalyzed enantioselective redox‐neutral three‐component coupling of aldehydes, sulfonamides, and terminal alkenes that provides formal imino–ene‐type products. Enabled by in situ sulfonyl imine generation and a chiral SIPHOS‐PE phosphoramidite ligand, the reaction furnishes N ‐sulfonyl homoallylic amines with high regioselectivity and excellent enantioselectivity. The method is most effective for aliphatic aldehydes and allylarene‐derived terminal alkenes, while functionalized allyl esters, allyl phosphonates, heteroaryl alkenes, and complex‐molecule‐derived substrates are also tolerated. Mechanistic experiments and DFT calculations are consistent with a nickelacycle‐mediated pathway involving imine/alkene oxidative cyclization. This work establishes a redox‐neutral asymmetric alkene–imine coupling manifold for the three‐component synthesis of enantioenriched homoallylic amines from readily available starting materials.