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<p>Chiral α-branched amines are privileged scaffolds in pharmaceuticals and natural products, yet general methods for their direct asymmetric synthesis through α-C–H functionalization of amines remain challenging. Herein, we report a synergistic relay catalysis strategy merging heterogeneous palladium catalysis with homogeneous rhodium catalysis for the direct enantioselective α-arylation and alkenylation of <i>N</i>-sulfonyl amines. This approach merges heterogeneous palladium catalysis for <i>N</i>-sulfonyl amine desaturation using low-cost bromobenzene as a mild H-acceptor and homogeneous rhodium catalysis for enantioselective addition to the transient <i>N</i>-sulfonyl imine intermediate. Overcoming challenges of the compatibility between distinct catalytic modes and background reaction via palladium catalysis, the method provides access to a broad range of enantioenriched α-diaryl, α-alkylaryl, and α-alkenylaryl amines in high yields (up to 98%) and enantioselectivities (up to 99.5% ee). Furthermore, the strategy is successfully extended to the enantioselective synthesis of 6-aryl-5,6-dihydrophenanthridines via a subsequent light-mediated radical cyclization.</p>

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Enantioselective α-aryl/alkenylation of N-sulfonyl amines via relay heterogeneous and homogeneous Pd/Rh catalysis

  • 期刊论文

  • 发表日期：

    2026年5月14日

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  • Yu-Cheng Liu,
  • Jia-Yue Li,
  • Zi-Qiao Wang,
  • Lun Li,
  • Yu-Long Li

摘要

Chiral α-branched amines are privileged scaffolds in pharmaceuticals and natural products, yet general methods for their direct asymmetric synthesis through α-C–H functionalization of amines remain challenging. Herein, we report a synergistic relay catalysis strategy merging heterogeneous palladium catalysis with homogeneous rhodium catalysis for the direct enantioselective α-arylation and alkenylation of N-sulfonyl amines. This approach merges heterogeneous palladium catalysis for N-sulfonyl amine desaturation using low-cost bromobenzene as a mild H-acceptor and homogeneous rhodium catalysis for enantioselective addition to the transient N-sulfonyl imine intermediate. Overcoming challenges of the compatibility between distinct catalytic modes and background reaction via palladium catalysis, the method provides access to a broad range of enantioenriched α-diaryl, α-alkylaryl, and α-alkenylaryl amines in high yields (up to 98%) and enantioselectivities (up to 99.5% ee). Furthermore, the strategy is successfully extended to the enantioselective synthesis of 6-aryl-5,6-dihydrophenanthridines via a subsequent light-mediated radical cyclization.