<p>Chiral <i>N</i>-spiroheterocycles are privileged yet synthetically challenging scaffolds for ligands, functional materials, and drug discovery. Here we show a cobalt-catalyzed asymmetric migratory dearomative annulation of electron-deficient <i>N</i>‑heteroarenes for their construction. The success of this transformation hinges on a dynamic ligand relay catalysis strategy, wherein two distinct ligands work in tandem: one facilitates a 1,4-cobalt/hydride shift, and the other governs the enantioselective dearomative annulation, delivering chiral <i>N</i>-spiroheterocycles with high efficiency and selectivity.</p>

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Ligand relay catalysis enables asymmetric migratory dearomative annulation of N-heteroarenes

  • Zhiyong Song,
  • Xinyu Li,
  • Xinchen Wang,
  • Asif Rasool,
  • You Wang,
  • Shaolin Zhu

摘要

Chiral N-spiroheterocycles are privileged yet synthetically challenging scaffolds for ligands, functional materials, and drug discovery. Here we show a cobalt-catalyzed asymmetric migratory dearomative annulation of electron-deficient N‑heteroarenes for their construction. The success of this transformation hinges on a dynamic ligand relay catalysis strategy, wherein two distinct ligands work in tandem: one facilitates a 1,4-cobalt/hydride shift, and the other governs the enantioselective dearomative annulation, delivering chiral N-spiroheterocycles with high efficiency and selectivity.