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<p>Transition-metal-catalysed migratory cross-coupling reactions have emerged as a powerful tool for the creation of new C–C bonds. Advances have recently been made in nickel-catalysed migratory cross-coupling where a two-electron β-hydride elimination–migratory insertion pathway takes place; however, asymmetric migratory cross-couplings, which proceed with a heteroatom-based group migration, still remain challenging. Here we report a nickel-catalysed coupling reaction of amino alcohol-derived sulfonates with a variety of carbon-based electrophiles, enabled by a radical 1,2-amino migration process. Notably, the modified chiral Bilm ligands were the key factor in achieving high stereoselectivity and reactivity. A wide range of enantioenriched 2-alkyl-, alkenyl- and aryl-substituted β-arylethylamines have been accessed. The synthetic potential of this transformation is demonstrated by the synthesis of chiral precursors of drug molecules, such as venlafaxine and preclamol. Preliminary mechanistic studies suggest that gradual tosylate–iodide exchange, the formation of benzyl radical species through homolysis of Ni–C bonds and radical 1,2-amino migration are important for this transformation.</p><p></p>

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Nickel-catalysed enantioselective migratory reductive cross-coupling enabled by radical 1,2-amino migration

  • 期刊论文

  • 发表日期：

    2025年6月27日

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  • Xiaolin Ren,
  • Yiwei Qiao,
  • Bingqi Zhou,
  • Song Liu,
  • Yuan Huang

摘要

Transition-metal-catalysed migratory cross-coupling reactions have emerged as a powerful tool for the creation of new C–C bonds. Advances have recently been made in nickel-catalysed migratory cross-coupling where a two-electron β-hydride elimination–migratory insertion pathway takes place; however, asymmetric migratory cross-couplings, which proceed with a heteroatom-based group migration, still remain challenging. Here we report a nickel-catalysed coupling reaction of amino alcohol-derived sulfonates with a variety of carbon-based electrophiles, enabled by a radical 1,2-amino migration process. Notably, the modified chiral Bilm ligands were the key factor in achieving high stereoselectivity and reactivity. A wide range of enantioenriched 2-alkyl-, alkenyl- and aryl-substituted β-arylethylamines have been accessed. The synthetic potential of this transformation is demonstrated by the synthesis of chiral precursors of drug molecules, such as venlafaxine and preclamol. Preliminary mechanistic studies suggest that gradual tosylate–iodide exchange, the formation of benzyl radical species through homolysis of Ni–C bonds and radical 1,2-amino migration are important for this transformation.