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Rate and Computational Studies for Pd-NHC-Catalyzed Amination with Primary Alkylamines and Secondary Anilines: Rationalizing Selectivity for Monoarylation versus Diarylation with NHC Ligands |
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| Authors: | Christopher Lombardi Dr Richard P Rucker Dr Robert D J Froese Dr Sepideh Sharif Prof Pier Alexandre Champagne Prof Michael G Organ |
| Institution: | 1. Department of Chemistry, York University, 4700 Keele St, Toronto, ON, M3J 1P3 Canada;2. Core R&D, The DOW Chemical Company, Midland, MI, 48647 USA;3. Department of Chemistry, York University, 4700 Keele St, Toronto, ON, M3J 1P3 Canada
Centre for Catalysis Research and Innovation (CCRI), Department of Chemistry and Biomolecular Sciences, University of Ottawa, 75 Laurier Ave East, Ottawa, ON, K1N 6N5 Canada;4. Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ, 07102 USA Centre for Catalysis Research and Innovation (CCRI), Department of Chemistry and Biomolecular Sciences, University of Ottawa, 75 Laurier Ave East, Ottawa, ON, K1N 6N5 Canada |
| Abstract: | The relative rates of arylation of primary alkylamines with different Pd-NHC catalysts have been measured, as have the relative rates of arylation of the secondary aniline product in an attempt to understand the key ligand design features necessary to have high selectivity for the monoarylated amine product. As the substituents on the N-aryl ring of the NHC increase in size, selectivity for monoarylation increases and this is further enhanced by chlorinating the back of the NHC ring. Computations have been performed on the catalytic cycle of this transformation in order to understand the selectivity obtained with the different catalysts. |
| Keywords: | amination catalysis cross-coupling PEPPSI rate study selective |