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Desperately Seeking For The Catalytic Species In Suzuki-Miyaura Reaction

Abstract : The use of ligand-free supported Pd is an attractive idea because it avoids problems related to the presence of the ligands (cost and toxicity). Also the catalyst is easily recovered at the end of the reaction by conventional methods such as filtration or decantation. Thus, it is easier to meet regulations in Active Pharmaceutical Ingredients (<10 ppm). However, the presence of molecular or atomic Pd species in solution when using solid catalysts has created an important discussion on the true nature of catalysis. This last could be heterogeneous on the surface of the supported Pd or homogeneous via species in solution. In this work the Suzuki-Miyaura (SM) reaction was chosen as the target reaction. In the absence of an overall kinetic study in the literature, a kinetic study was carried out with a molecular catalyst. It provided a mechanistic law that represents the homogeneous part of the reaction. Furthermore, an innovative test (“split flow reactor”) has been proposed. It permits to distinguish between the homogeneous and heterogeneous contributions and to determine the nature of the species that catalyze the reaction. It was used in the reaction of different iodo, bromo, and chloro aryls. Several supported catalysts were used by varying the nature of the support and the oxidation state of Pd (Pd (0) and Pd (II)) in the initial precursor. Finally, a reactor model has shown that for the same iodoaryl, whatever the nature of the solid, the supported Pd seems to release the same active species in solution. These species catalyze the SM reaction with initial activities of the order of 500 000 h-1. The split flow reactor is a new, easy-to-use test. Accompanied with online analysis techniques, it can be used to track the evolution of catalytic species in real time and to study other chemical systems
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Amine Bourouina. Desperately Seeking For The Catalytic Species In Suzuki-Miyaura Reaction. Chemical and Process Engineering. Université de Lyon, 2019. English. ⟨NNT : 2019LYSE1258⟩. ⟨tel-02482607⟩

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