Metal‐Controlled Enantiodivergent Tandem Rearrangement to Synthesize 2 H ‐Azirines

作者：Zhendong Yang, Maoping Pu, Liangkun Yang, Yuqiao Zhou, Hongda Wu, Bosheng Wang, Xiaoming Feng, Xiaohua Liu · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202505725 · 被引用次数：17 · 研究领域：Synthesis and Catalytic Reactions、Catalytic C–H Functionalization Methods、Cyclopropane Reaction Mechanisms

A metal-controlled enantiodivergent rearrangement of α-diazo-β-keto oxime ethers has been developed. Switching the metal catalyst from Co(II) to Fe(II) with an identical ligand completely reverses the asymmetric induction. Both enantiomers of chiral 2H-azirines and its derivatives are accessible under thermal or photolytic conditions. The cobalt-based reaction is highly efficient even at 0.05 mol% catalyst loading. Mechanistic studies, including kinetic experiments and density functional theory calculations, reveal that distinct electronic properties of cobalt and iron modulate intermediate conformations, thereby altering the enantioselectivity.