Work

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

Year: 2026

Type: article

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.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.8922921

Authors: Ye‐Wei Huang, Yue‐Na Duan, Tianze Zhang, Qi‐Lin Zhou, Li‐Jun Xiao

Institutions: Nankai University, State Key Laboratory of Elemental Organic Chemistry

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: bronze

Funders: National Natural Science Foundation of China, National Key Research and Development Program of China, Fundamental Research Funds for the Central Universities

Awards: G2947838994, G3100623411, G4599070506, G4890951106