Oxy-pyridinium Ylides Mediated 1,4-Pyridyl/Aryl Translocation
Molecular rearrangement via carbene transfer is a powerful tool to access molecular diversity. Herein, we describe an efficient approach to selective pyridyl/aryl relocation via a rhodium-catalyzed aminoarylation of diazo compounds, providing a promising strategy to access <i>ortho</i>-pyridyl N-alkylated pyridone scaffolds in a single operation. This reaction features the novel reactivity of oxy-pyridinium ylide, rhodium-associated five-membered transition state, and 1,4-pyridyl/aryl relocation. A computational study discloses the initial oxy-pyridinium ylide formation, keto-enol tautomerization, and 1,4-pyridyl migration to complete the whole rearrangement.
Authors
- Jiangtao Sun (ORCID: https://orcid.org/0000-0003-2516-3466)
- Meirong Huang (ORCID: https://orcid.org/0000-0002-3489-9929)
- Xinhao Zhang (ORCID: https://orcid.org/0000-0002-8210-2531)
- Shengbiao Tang (ORCID: https://orcid.org/0000-0003-4860-5458)
- Zichun Yan (ORCID: https://orcid.org/0009-0006-4123-6644)
- Yaping Tang
Institutions
- Peking University (CN)
- Shenzhen Bay Laboratory (CN)
- Changzhou University (CN)
Publication Details
- Journal
- Organic Letters
- Published
- 2024-11-11
- DOI
- https://doi.org/10.1021/acs.orglett.4c03656
- Citations
- 1
- Primary Topic
- Cyclopropane Reaction Mechanisms
- Type
- article
- Field-Weighted Citation Impact
- 0.25
Funders
- National Natural Science Foundation of China
- Natural Science Foundation of Jiangsu Province
- Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology Department
- Special Project for Research and Development in Key areas of Guangdong Province