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<p>Dirhodium(II) complexes have achieved great success in organic synthesis, and fine-tuning their catalytic properties with various bridging ligands is well-investigated in carbene chemistry. However, combining dirhodium(II) with a sophisticated ligand as a catalyst in other reactions is still extremely challenging, especially for the asymmetric synthesis of valuable chiral molecules. Herein, we report a dirhodium(II)/(S)-MeO-BIPHEP catalytic system for the challenging asymmetric β-alkenylation of α,β-unsaturated aldehydes, affording the corresponding chiral conjugate addition products in good yields with high enantioselectivities. A couple of drug-derived substrates were also compatible with the protocol, which has been successfully used to prepare biologically relevant pyranochromene compounds. Preliminary mechanistic studies suggested that the dirhodium core might remain intact over the catalytic cycle, and the chiral diphosphine ligand plays a key role in this novel reactivity and determining the high enantioselectivities of the asymmetric conjugate addition.</p>

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Enantioselective β-alkenylation of α,β-unsaturated aldehydes via chiral biphosphine ligand modified dirhodium(II) catalysis

  • 期刊论文

  • 发表日期：

    2025年1月9日

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  • Guangli Xu,
  • Hongda Chen,
  • Xiaoming Wang

摘要

Dirhodium(II) complexes have achieved great success in organic synthesis, and fine-tuning their catalytic properties with various bridging ligands is well-investigated in carbene chemistry. However, combining dirhodium(II) with a sophisticated ligand as a catalyst in other reactions is still extremely challenging, especially for the asymmetric synthesis of valuable chiral molecules. Herein, we report a dirhodium(II)/(S)-MeO-BIPHEP catalytic system for the challenging asymmetric β-alkenylation of α,β-unsaturated aldehydes, affording the corresponding chiral conjugate addition products in good yields with high enantioselectivities. A couple of drug-derived substrates were also compatible with the protocol, which has been successfully used to prepare biologically relevant pyranochromene compounds. Preliminary mechanistic studies suggested that the dirhodium core might remain intact over the catalytic cycle, and the chiral diphosphine ligand plays a key role in this novel reactivity and determining the high enantioselectivities of the asymmetric conjugate addition.