التفاصيل البيبلوغرافية
| العنوان: |
Asymmetric transfer hydrogenation of ketones catalyzed by chiral macrocyclic cobalt(II) complexes. |
| المؤلفون: |
Ruan, Sun-Hong1 (AUTHOR), Fan, Zi-Wei1 (AUTHOR), Zhang, Wen-Jing1 (AUTHOR), Xu, Han1 (AUTHOR), An, Dong-Li1 (AUTHOR), Wei, Zan-Bin1 (AUTHOR), Yuan, Ru-Ming1 (AUTHOR) yuanrm@xmu.edu.cn, Gao, Jing-Xing1 (AUTHOR), Li, Yan-Yun1 (AUTHOR) yanyunli@xmu.edu.cn |
| المصدر: |
Journal of Catalysis. Feb2023, Vol. 418, p100-109. 10p. |
| مصطلحات موضوعية: |
*TRANSFER hydrogenation, *COBALT, *DENSITY functional theory, *METALWORK, *METAL catalysts, *KETONES |
| مستخلص: |
Novel chiral macrocyclic cobalt(II) complexes could be conveniently prepared and their structures were determined by X-ray diffraction method. The ATH of ketones catalyzed by cobalt(II) complex proceeded smoothly with high ee. Furthermore, DFT calculation accounts for the high catalytic performances of cobalt(II) catalyst. [Display omitted] • Novel chiral macrocyclic cobalt(II) complexes could be conveniently prepared. • The structures of cobalt(II) complexes were determined by X-ray diffraction method. • ATH of ketones catalyzed by cobalt(II) complex proceeded smoothly with high ee. • DFT calculation accounts for the high catalytic performances of cobalt(II) catalyst. • It represents an attractive direction for development of novel cheap metal catalyst. Using easily available CoBr 2 and chiral cyclic P x N y -type ligands as starting materials, novel chiral cyclic cobalt(II) complexes could be conveniently prepared. Furthermore, we obtained the single crystals suitable for X-ray diffraction to confirm the structures of these cobalt(II) complexes. The asymmetric transfer hydrogenation (ATH) of ketones catalyzed by these well-designed cobalt(II) complexes was investigated. Among them, cobalt(II) complex containing chiral macrocyclic iminophosphine ligand CyP 2 N 4 exhibited high catalytic activity and enantioselectivity (up to 99% ee). Density functional theory (DFT) calculations suggested that cobalt(II) complex (R , R , R' , R')-CyP 2 N 4 -Co(II) (C1) is easier to form metal hydride, which is the key intermediate during the enantioselective transfer hydrogenation reaction. Study results also revealed that the unique macrocyclic structure of complex C1 could form a special microenvironment around cobalt ion. Therefrom the substrate coordinated with the central metal along this specific reaction channel during the asymmetric catalytic reaction, resulting high enantioselectivity. [ABSTRACT FROM AUTHOR] |
| قاعدة البيانات: |
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