Chiral Phosphoric Acid and BF <sub>3</sub> ·THF Relay Catalytic System Enables a Formal Asymmetric Aza-Baeyer–Villiger Rearrangement
A relay catalytic system comprising chiral phosphoric acid (CPA) and BF<sub>3</sub>·THF enables a formal asymmetric aza-Baeyer-Villiger rearrangement of cyclobutanones with a newly designed dinaphthylphosphinyl hydroxylamine (DNPH) reagent. The strategy combines the highly enantioselective CPA-catalyzed condensation of cyclobutanones with DNPH (generally >90% ee) and BF<sub>3</sub>·THF-promoted Beckmann rearrangement involving an axial-to-point chirality transfer with excellent enantiospecificity (>98% es). This one-pot method offers operational simplicity and excellent enantiocontrol, facilitating the synthesis of valuable γ-lactams.
Authors
- Ping Tian (ORCID: https://orcid.org/0000-0002-5612-0664)
- Qinghua Li
- Yiwen Zhao (ORCID: https://orcid.org/0000-0002-7228-6859)
- Yao Lu (ORCID: https://orcid.org/0000-0001-6784-8303)
- Xi‐Liang Liu
- Shu‐Hui Li
Institutions
- Shanghai University of Traditional Chinese Medicine (CN)
Publication Details
- Journal
- Organic Letters
- Published
- 2025-12-20
- DOI
- https://doi.org/10.1021/acs.orglett.5c04821
- Citations
- 1
- Primary Topic
- Asymmetric Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.94