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

Song, Zhiyong; Li, Xinyu; Wang, Xinchen; Rasool, Asif; Wang, You; Zhu, Shaolin · Nat Commun · 2026

basic_science · Level V

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Abstract

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.