Studies on the Amination of Aryl Chlorides with a Monoligated Palladium Catalyst: Kinetic Evidence for a Cooperative Mechanism |
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| Authors: | Dr Ciril Jimeno Dr Ute Christmann Eduardo C Escudero‐Adán Prof Ramon Vilar Prof Miquel A Pericàs |
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| Institution: | 1. Department of Biological Chemistry and Molecular Modelling, Institute of Advanced Chemistry of Catalonia (IQAC‐CSIC), Jordi Girona 18‐26, 08034 Barcelona (Spain);2. Institute of Chemical Research of Catalonia (ICIQ), Av. Pa?sos Catalans 16, 43007 Tarragona (Spain);3. Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ (UK);4. Departament de Química Orgànica, Universitat de Barcelona, Martí i franquès 1‐11, 08028 Barcelona (Spain) |
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| Abstract: | Combined spectroscopic, crystallographic, and kinetic studies of the mechanism of aromatic amination with the efficient dinuclear Pd precatalyst Pd2Cl(μ‐Cl)PtBu2(Bph‐Me)] (Bph‐Me=2′‐methyl‐1,1′‐biphenyl]‐2‐yl) have revealed overlapping, yet cooperative, mechanistic scenarios, the relative weights of which are strongly influenced by the products formed as the reaction proceeds. The stability and evolution of the precatalyst in solution has been studied and several metalation pathways that point to a single monoligated intermediate have been identified. Our work sheds light on the nature of the catalytic species involved in the process and on the structure of the corresponding catalytic network. |
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| Keywords: | amination C?H activation cross‐coupling palladium reaction mechanisms |
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