Divergent Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0) Enables Chemoselective Trifluoromethylselenolation
| Autor: | Franziska Schoenebeck, Henry C. Fisher, Indrek Kalvet, Alexander B. Dürr, Khai Nghi Truong |
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| Rok vydání: | 2017 |
| Předmět: |
Dinuclear Catalysts
Dimer chemistry.chemical_element 010402 general chemistry Medicinal chemistry 01 natural sciences Catalysis nickel chemistry.chemical_compound fluorine Organic chemistry Reactivity (chemistry) Chemoselectivity 010405 organic chemistry Chemistry Communication Aryl General Medicine General Chemistry Combinatorial chemistry Communications 0104 chemical sciences 3. Good health Nickel chemoselectivity density functional calculations Fluorine |
| Zdroj: | Angewandte Chemie (International Ed. in English) Angewandte Chemie International Edition |
| ISSN: | 1433-7851 |
| DOI: | 10.1002/anie.201706423 |
| Popis: | We herein showcase the ability of NHC-derived dinuclear Ni(I)-Ni(I) complexes to override fundamental reactivity limits of mononuclear (NHC)Ni(0) catalysts in cross-coupling. This is demonstrated with the development of a chemoselective Ni(I) dimer-catalyzed trifluoromethylselenolation of aryl iodides. A novel SeCF3-bridged dinuclear Ni(I) dimer was isolated and shown to be selectively reactive with Ar-I bonds. Our computational and experimental reactivity data suggest dinuclear Ni(I) catalysis to be operative. The corresponding Ni(0) on the other hand suffers from preferred reaction with the product, ArSeCF3, over productive cross-coupling and is hence inactive. |
| Databáze: | OpenAIRE |
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