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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| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
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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| Summary: | 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. |
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| ISSN: | 2041-1723 |