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

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.