Chiral Spirobipyridine Synthesis by Cobalt-Catalyzed Enantioselective Double [2 + 2 + 2] Cycloaddition
Ke Li
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorDanyang Zhu
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorLuyu Cao
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Changkun Li
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
E-mail: [email protected]
Search for more papers by this authorKe Li
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorDanyang Zhu
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorLuyu Cao
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Changkun Li
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
E-mail: [email protected]
Search for more papers by this authorGraphical Abstract
We report a cobalt-catalyzed enantioselective double [2 + 2 + 2] cycloaddition between bisalkynyl malononitriles and terminal alkynes. Chiral spirobipyridines bearing ortho- and meta-substituents can be synthesized with the help of chiral bisoxazolinephosphine ligands.
Abstract
Chiral spirobiindanes are recognized as the privileged structures in the field of asymmetric catalysis. However, the structurally similar chiral spirobipyridines have not yet been explored as chiral ligands or organocatalysts due to the absence of efficient synthetic methods. Herein, we report a cobalt-catalyzed enantioselective synthesis of spirobipyridines via double [2 + 2 + 2] cycloaddition reaction. Spirobipyridines with ortho- or meta-substituents could be obtained with exclusive regioselectivity and up to 99% ee in the presence of cobalt and bisoxazolinephosphine ligands. Spirobipyridines coordinate with transition metals as chiral ligands. Spirobipyridine dioxides can be applied as chiral organocatalysts in the asymmetric allylation of aldehydes.
Conflict of Interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the Supporting Information of this article.
Supporting Information
| Filename | Description |
|---|---|
| anie202504831-sup-0001-SuppMatS1.pdf18.3 MB | Supporting Information |
| anie202504831-sup-0002-SuppMatS2.zip1.6 MB | Supporting Information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
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