Geminal Aminocyanation Enabled by Ylide Mediated Rearrangement
Herein, we describe experimental and computational studies to understand the features of oxycyanopyridinium ylides generated in situ from oxy-cyanopyridines and rhodium carbene. This chemistry has enabled the concomitant formation of both C-N and C-C bonds, providing a complementary approach for cyanation reactions. Density functional theory calculations indicate the sequential metal-bound ylide formation, rhodium-associated five-membered transition state, and 1,4-cyano group relocation. Moreover, the enantioselective rearrangement has been realized by using chiral dirhodium complexes as the catalysts.
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)
- Chuang Wang (ORCID: https://orcid.org/0009-0001-6116-2404)
- Zichun Yan (ORCID: https://orcid.org/0009-0006-4123-6644)
Institutions
- Peking University (CN)
- Shenzhen Bay Laboratory (CN)
- Changzhou University (CN)
Publication Details
- Journal
- Organic Letters
- Published
- 2024-11-25
- DOI
- https://doi.org/10.1021/acs.orglett.4c03797
- Primary Topic
- Cyclopropane Reaction Mechanisms
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Natural Science Foundation of China
- Natural Science Foundation of Jiangsu Province
- Changzhou University
- Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology Department
- Special Project for Research and Development in Key areas of Guangdong Province