Iron-catalyzed alkyne alkylzincation affected by counterions
Abstract Metal complex catalysts typically comprise three components: ligands, central metals, and counterions. The counterion profoundly influences the activity and selectivity of numerous catalytic reactions, while such a phenomenon is rarely observed in carbozincation reactions. Herein, we discov...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-08-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-62460-z |
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| author | Lu-Jie Li Qiao Zhang Peng He Ming-Yao Huang Shou-Fei Zhu |
| author_facet | Lu-Jie Li Qiao Zhang Peng He Ming-Yao Huang Shou-Fei Zhu |
| author_sort | Lu-Jie Li |
| collection | DOAJ |
| description | Abstract Metal complex catalysts typically comprise three components: ligands, central metals, and counterions. The counterion profoundly influences the activity and selectivity of numerous catalytic reactions, while such a phenomenon is rarely observed in carbozincation reactions. Herein, we discover that the catalytic efficiency of iron-catalyzed alkylzincation of alkynes is markedly enhanced when the weakly coordinating bulky counterion tetrakis(3,5-bis(trifluoromethyl)phenyl)borate ([BArF 4]−) is incorporated into the reaction. This approach yields ionic iron catalysts with exceptional activity (up to 32,900 TON), regioselectivity (mostly >95:5), and stereoselectivity (mostly >95:5) in both alkylzincation reactions of terminal and internal alkynes. Notably, the methylzincation of non-activated terminal and internal alkynes is rendered feasible. This methodology also enables the efficient synthesis of a diverse array of biologically active molecules and their key intermediates. Mechanistic investigations suggest that a cationic Fe(II) species serves as the active catalytic species and the weakly coordinating bulky counterion stabilizes a cationic iron(II) alkyl complex without competing with the alkyne substrate. |
| format | Article |
| id | doaj-art-1998df7bc1ff45dfb43fce41920ee3f7 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-08-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-1998df7bc1ff45dfb43fce41920ee3f72025-08-20T03:43:22ZengNature PortfolioNature Communications2041-17232025-08-0116111210.1038/s41467-025-62460-zIron-catalyzed alkyne alkylzincation affected by counterionsLu-Jie Li0Qiao Zhang1Peng He2Ming-Yao Huang3Shou-Fei Zhu4Academy for Advanced Interdisciplinary Studies, Frontiers Science Center for New Organic Matter, State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai UniversityAcademy for Advanced Interdisciplinary Studies, Frontiers Science Center for New Organic Matter, State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai UniversityAcademy for Advanced Interdisciplinary Studies, Frontiers Science Center for New Organic Matter, State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai UniversityAcademy for Advanced Interdisciplinary Studies, Frontiers Science Center for New Organic Matter, State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai UniversityAcademy for Advanced Interdisciplinary Studies, Frontiers Science Center for New Organic Matter, State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai UniversityAbstract Metal complex catalysts typically comprise three components: ligands, central metals, and counterions. The counterion profoundly influences the activity and selectivity of numerous catalytic reactions, while such a phenomenon is rarely observed in carbozincation reactions. Herein, we discover that the catalytic efficiency of iron-catalyzed alkylzincation of alkynes is markedly enhanced when the weakly coordinating bulky counterion tetrakis(3,5-bis(trifluoromethyl)phenyl)borate ([BArF 4]−) is incorporated into the reaction. This approach yields ionic iron catalysts with exceptional activity (up to 32,900 TON), regioselectivity (mostly >95:5), and stereoselectivity (mostly >95:5) in both alkylzincation reactions of terminal and internal alkynes. Notably, the methylzincation of non-activated terminal and internal alkynes is rendered feasible. This methodology also enables the efficient synthesis of a diverse array of biologically active molecules and their key intermediates. Mechanistic investigations suggest that a cationic Fe(II) species serves as the active catalytic species and the weakly coordinating bulky counterion stabilizes a cationic iron(II) alkyl complex without competing with the alkyne substrate.https://doi.org/10.1038/s41467-025-62460-z |
| spellingShingle | Lu-Jie Li Qiao Zhang Peng He Ming-Yao Huang Shou-Fei Zhu Iron-catalyzed alkyne alkylzincation affected by counterions Nature Communications |
| title | Iron-catalyzed alkyne alkylzincation affected by counterions |
| title_full | Iron-catalyzed alkyne alkylzincation affected by counterions |
| title_fullStr | Iron-catalyzed alkyne alkylzincation affected by counterions |
| title_full_unstemmed | Iron-catalyzed alkyne alkylzincation affected by counterions |
| title_short | Iron-catalyzed alkyne alkylzincation affected by counterions |
| title_sort | iron catalyzed alkyne alkylzincation affected by counterions |
| url | https://doi.org/10.1038/s41467-025-62460-z |
| work_keys_str_mv | AT lujieli ironcatalyzedalkynealkylzincationaffectedbycounterions AT qiaozhang ironcatalyzedalkynealkylzincationaffectedbycounterions AT penghe ironcatalyzedalkynealkylzincationaffectedbycounterions AT mingyaohuang ironcatalyzedalkynealkylzincationaffectedbycounterions AT shoufeizhu ironcatalyzedalkynealkylzincationaffectedbycounterions |