Atroposelective hydroarylation of biaryl phosphines directed by phosphorus centres
Abstract Prized for their ability to generate chemical complexity rapidly, catalytic carbon–hydrogen (C–H) activation and functionalization reactions have enabled a paradigm shift in the standard logic of synthetic chemistry. Directing group strategies have been used extensively in C–H activation re...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-12-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-44202-1 |
| _version_ | 1827399395747823616 |
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| author | Zexian Li Minyan Wang Youqing Yang Yong Liang Xiangyang Chen Yue Zhao K. N. Houk Zhuangzhi Shi |
| author_facet | Zexian Li Minyan Wang Youqing Yang Yong Liang Xiangyang Chen Yue Zhao K. N. Houk Zhuangzhi Shi |
| author_sort | Zexian Li |
| collection | DOAJ |
| description | Abstract Prized for their ability to generate chemical complexity rapidly, catalytic carbon–hydrogen (C–H) activation and functionalization reactions have enabled a paradigm shift in the standard logic of synthetic chemistry. Directing group strategies have been used extensively in C–H activation reactions to control regio- and enantioselectivity with transition metal catalysts. However, current methods rely heavily on coordination with nitrogen and/or oxygen atoms in molecules and have therefore been found to exhibit limited generality in asymmetric syntheses. Here, we report enantioselective C–H activation with unsaturated hydrocarbons directed by phosphorus centres to rapidly construct libraries of axially chiral phosphines through dynamic kinetic resolution. High reactivity and enantioselectivity are derived from modular assembly of an iridium catalyst with an endogenous phosphorus atom and an exogenous chiral phosphorus ligand, as confirmed by detailed experimental and computational studies. This reaction mode significantly expands the pool of enantiomerically enriched functional phosphines, some of which have shown excellent efficiency for asymmetric catalysis. |
| first_indexed | 2024-03-08T19:45:21Z |
| format | Article |
| id | doaj.art-644b178939ef4fd5870c2fe9079fa16a |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-08T19:45:21Z |
| publishDate | 2023-12-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-644b178939ef4fd5870c2fe9079fa16a2023-12-24T12:24:02ZengNature PortfolioNature Communications2041-17232023-12-0114111010.1038/s41467-023-44202-1Atroposelective hydroarylation of biaryl phosphines directed by phosphorus centresZexian Li0Minyan Wang1Youqing Yang2Yong Liang3Xiangyang Chen4Yue Zhao5K. N. Houk6Zhuangzhi Shi7Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Huaibei Normal UniversityState Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing UniversityKey Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Huaibei Normal UniversityState Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing UniversityDepartment of Chemistry and Biochemistry, University of CaliforniaState Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing UniversityDepartment of Chemistry and Biochemistry, University of CaliforniaKey Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Huaibei Normal UniversityAbstract Prized for their ability to generate chemical complexity rapidly, catalytic carbon–hydrogen (C–H) activation and functionalization reactions have enabled a paradigm shift in the standard logic of synthetic chemistry. Directing group strategies have been used extensively in C–H activation reactions to control regio- and enantioselectivity with transition metal catalysts. However, current methods rely heavily on coordination with nitrogen and/or oxygen atoms in molecules and have therefore been found to exhibit limited generality in asymmetric syntheses. Here, we report enantioselective C–H activation with unsaturated hydrocarbons directed by phosphorus centres to rapidly construct libraries of axially chiral phosphines through dynamic kinetic resolution. High reactivity and enantioselectivity are derived from modular assembly of an iridium catalyst with an endogenous phosphorus atom and an exogenous chiral phosphorus ligand, as confirmed by detailed experimental and computational studies. This reaction mode significantly expands the pool of enantiomerically enriched functional phosphines, some of which have shown excellent efficiency for asymmetric catalysis.https://doi.org/10.1038/s41467-023-44202-1 |
| spellingShingle | Zexian Li Minyan Wang Youqing Yang Yong Liang Xiangyang Chen Yue Zhao K. N. Houk Zhuangzhi Shi Atroposelective hydroarylation of biaryl phosphines directed by phosphorus centres Nature Communications |
| title | Atroposelective hydroarylation of biaryl phosphines directed by phosphorus centres |
| title_full | Atroposelective hydroarylation of biaryl phosphines directed by phosphorus centres |
| title_fullStr | Atroposelective hydroarylation of biaryl phosphines directed by phosphorus centres |
| title_full_unstemmed | Atroposelective hydroarylation of biaryl phosphines directed by phosphorus centres |
| title_short | Atroposelective hydroarylation of biaryl phosphines directed by phosphorus centres |
| title_sort | atroposelective hydroarylation of biaryl phosphines directed by phosphorus centres |
| url | https://doi.org/10.1038/s41467-023-44202-1 |
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