Selective 1,2‐Aryl‐Aminoalkylation of Alkenes Enabled by Metallaphotoredox Catalysis

• Published in: Angewandte Chemie International Edition 2020-10, Vol.59 (41), p.17910-17916
• Main Authors: Zheng, Songlin, Chen, Zimin, Hu, Yuanyuan, Xi, Xiaoxiang, Liao, Zixuan, Li, Weirong, Yuan, Weiming
• Format: Article
• Language: English
• Subjects: 1,2-dicarbofunctionalization; Alkenes; Amines; Amino acids; Aromatic compounds; Cascade chemical reactions; Catalysis; conjunctive cross-coupling; Cross coupling; Electron transfer; Functional groups; metallaphotoredox catalysis; Nickel; Radicals; Single electrons; three-component reactions
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202006439

A highly chemo‐ and regioselective intermolecular 1,2‐aryl‐aminoalkylation of alkenes by photoredox/nickel dual catalysis is described here. This three‐component conjunctive cross‐coupling is highlighted by its first application of primary alkyl radicals, which were not compatible in previous reports. The readily prepared α‐silyl amines could be transferred to α‐amino radicals by photo‐induced single electron transfer step. The radical addition/cross‐coupling cascade reaction proceeds under mild, base‐free and redox‐neutral conditions with good functional group tolerance, and importantly, provides an efficient and concise method for the synthesis of structurally valuable α‐aryl substituted γ‐amino acid derivatives motifs. A photoredox/nickel dual catalyzed three‐component conjunctive cross‐coupling of alkenes with α‐silyl amines and aryl halides is reported. Primary alkyl radicals can be applied in the three‐component dicarbofunctionalization (DCF) of a π‐bond system. The base‐free, redox‐neutral conditions, the broad substrate scope, and functional group compatibility allow to synthesize structurally valuable α‐aryl substituted γ‐amino acid moieties.