CC-kupplungen von CO2 mit 1,3-dienen an eisen(0)-komplexen; carboxylatbildung und folgereaktionen |
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| Institution: | 1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China;2. University of Chinese Academy of Sciences, Beijing 100049, China;1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock (LIKAT Rostock), Albert-Einstein-Straße 29a, 18059, Rostock, Germany;2. Institut für Biochemie, Ernst-Moritz-Arndt-Universität Greifswald, Felix-Hausdorff-Str. 4, 17487, Greifswald, Germany;3. Department of Chemistry, Materials and Chemical Engineering “G. Natta”, Politecnico di Milano, Piazza L. da Vinci 32, 20133, Milano, Italy;1. CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, PR China;2. Xiamen Institute of Rare-earth Materials, Haixi Institutes, Chinese Academy of Sciences, Fujian 361005, PR China;3. Medical College, Xiamen University, Xiamen, Fujian 361102, PR China;1. Department of Chemical Engineering, Laval University, Quebec, G1V0A6, Canada;2. Laboratory of Advanced Materials, Department of Chemistry, Fudan University, Shanghai, 200433, China |
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| Abstract: | 1,3-Dienes react with CO2 at ligand-iron(0) systems to form η3-allyl carboxylates. The dynamic allylic system is influenced by addition of further ligands such as phosphanes or maleic acid anhydride or acetic acid anhydride. The direction of this influence is shown on the basis of the products generated by protonolysis or insertion of CO2. When substituted 1,3-dienes are used, the 1/1 coupling step is regioselective. For example, with 1,3-pentadiene and CO2 only two η3-allyliron carboxylates in the molar ratio 1/1 are formed. This isomer ratio confirms that the coupling reaction is kinetically controlled. |
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