Metal‐Controlled Enantiodivergent Tandem Rearrangement to Synthesize 2 <i>H</i> ‐Azirines
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.
Authors
- Yuqiao Zhou (ORCID: https://orcid.org/0000-0003-3490-4182)
- Zhendong Yang (ORCID: https://orcid.org/0000-0001-8165-8389)
- Maoping Pu (ORCID: https://orcid.org/0000-0002-0745-9549)
- Binghe Wang (ORCID: https://orcid.org/0000-0002-2200-5270)
- Liangkun Yang (ORCID: https://orcid.org/0000-0003-0438-4921)
- Xiaoming Feng (ORCID: https://orcid.org/0000-0003-4507-0478)
- Xiaohua Liu (ORCID: https://orcid.org/0000-0001-9555-0555)
- Hongda Wu (ORCID: https://orcid.org/0000-0001-8846-6582)
Institutions
- Sichuan University (CN)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-04-26
- DOI
- https://doi.org/10.1002/anie.202505725
- Citations
- 11
- Primary Topic
- Synthesis and Catalytic Reactions
- Type
- article
- Field-Weighted Citation Impact
- 10.30
Funders
- National Natural Science Foundation of China
- Sichuan University
- National Key Research and Development Program of China