An unusual chiral-at-metal mechanism for BINOL-metal asymmetric catalysis
Abstract Chiral binaphthols (BINOL)-metal combinations serve as powerful catalysts in asymmetric synthesis. Their chiral induction mode, however, typically relies on multifarious non-covalent interactions between the substrate and the BINOL ligand. In this work, we demonstrate that the chiral-at-met...
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-56000-y |
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| author | Zhenxing Li Pengfei Chen Zhigang Ni Liuzhou Gao Yue Zhao Ranran Wang Congqing Zhu Guoqiang Wang Shuhua Li |
| author_facet | Zhenxing Li Pengfei Chen Zhigang Ni Liuzhou Gao Yue Zhao Ranran Wang Congqing Zhu Guoqiang Wang Shuhua Li |
| author_sort | Zhenxing Li |
| collection | DOAJ |
| description | Abstract Chiral binaphthols (BINOL)-metal combinations serve as powerful catalysts in asymmetric synthesis. Their chiral induction mode, however, typically relies on multifarious non-covalent interactions between the substrate and the BINOL ligand. In this work, we demonstrate that the chiral-at-metal stereoinduction mode could serve as an alternative mechanism for BINOL-metal catalysis, based on mechanistic studies of BINOL-aluminum-catalyzed asymmetric hydroboration of heteroaryl ketones. Theoretical calculations reveal that an octahedral stereogenic-at-metal aluminum alkoxide species is the most stable species within the reaction system, and also is the catalytic relevant intermediate, promoting the stereo-determining hydroboration reaction through a ligand-assisted hydride transfer mechanism rather than the conventional hydroalumination mechanism. These computations reproduce the experimental selectivities and also rationalize the stereoinduction mechanism, which arises from the aluminum-centered chirality induced by chiral BINOL ligands during diastereoselective assembly. The reliability of the proposed mechanism could be verified by the single-crystal X-ray diffraction characterization of the octahedral aluminum alkoxide complex. Additional NMR and Electronic Circular Dichroism (ECD) experiments elucidated the behavior of the hexacoordinated aluminum alkoxide in the solution phase. We anticipate that these findings will extend the applicability of BINOL-metal catalysis to a broader range of reactions. |
| format | Article |
| id | doaj-art-37c39dc8cbe5445f96621abab419875a |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
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| spelling | doaj-art-37c39dc8cbe5445f96621abab419875a2025-01-19T12:30:21ZengNature PortfolioNature Communications2041-17232025-01-0116111210.1038/s41467-025-56000-yAn unusual chiral-at-metal mechanism for BINOL-metal asymmetric catalysisZhenxing Li0Pengfei Chen1Zhigang Ni2Liuzhou Gao3Yue Zhao4Ranran Wang5Congqing Zhu6Guoqiang Wang7Shuhua Li8State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Nanjing UniversityState Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing UniversityCollege of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal UniversitySchool of Chemistry and Chemical Engineering, Yangzhou UniversityState Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing UniversityState Key Laboratory of Analytical Chemistry for Life Science, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing UniversityState Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing UniversityState Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Nanjing UniversityState Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Nanjing UniversityAbstract Chiral binaphthols (BINOL)-metal combinations serve as powerful catalysts in asymmetric synthesis. Their chiral induction mode, however, typically relies on multifarious non-covalent interactions between the substrate and the BINOL ligand. In this work, we demonstrate that the chiral-at-metal stereoinduction mode could serve as an alternative mechanism for BINOL-metal catalysis, based on mechanistic studies of BINOL-aluminum-catalyzed asymmetric hydroboration of heteroaryl ketones. Theoretical calculations reveal that an octahedral stereogenic-at-metal aluminum alkoxide species is the most stable species within the reaction system, and also is the catalytic relevant intermediate, promoting the stereo-determining hydroboration reaction through a ligand-assisted hydride transfer mechanism rather than the conventional hydroalumination mechanism. These computations reproduce the experimental selectivities and also rationalize the stereoinduction mechanism, which arises from the aluminum-centered chirality induced by chiral BINOL ligands during diastereoselective assembly. The reliability of the proposed mechanism could be verified by the single-crystal X-ray diffraction characterization of the octahedral aluminum alkoxide complex. Additional NMR and Electronic Circular Dichroism (ECD) experiments elucidated the behavior of the hexacoordinated aluminum alkoxide in the solution phase. We anticipate that these findings will extend the applicability of BINOL-metal catalysis to a broader range of reactions.https://doi.org/10.1038/s41467-025-56000-y |
| spellingShingle | Zhenxing Li Pengfei Chen Zhigang Ni Liuzhou Gao Yue Zhao Ranran Wang Congqing Zhu Guoqiang Wang Shuhua Li An unusual chiral-at-metal mechanism for BINOL-metal asymmetric catalysis Nature Communications |
| title | An unusual chiral-at-metal mechanism for BINOL-metal asymmetric catalysis |
| title_full | An unusual chiral-at-metal mechanism for BINOL-metal asymmetric catalysis |
| title_fullStr | An unusual chiral-at-metal mechanism for BINOL-metal asymmetric catalysis |
| title_full_unstemmed | An unusual chiral-at-metal mechanism for BINOL-metal asymmetric catalysis |
| title_short | An unusual chiral-at-metal mechanism for BINOL-metal asymmetric catalysis |
| title_sort | unusual chiral at metal mechanism for binol metal asymmetric catalysis |
| url | https://doi.org/10.1038/s41467-025-56000-y |
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