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Photooxidation of hypercoordinate silicate for the generation of carbon centered radicals : radical processes and dual catalysis

Abstract : Photoredox catalysis in visible light has succeeded in establishing itself as a gentle and eco-compatible method of formation of radical species, and more particularly of carbon radicals. Although this catalysis has proved to be efficient for the formation of carbon-carbon/heteroatom bonds, the generated carbon centered radicals are oftenverystabilized.Conversely, bis-catecholato silicates have shown to be capable of generating alkyl radicals that are not stabilized by photooxidation using polypyridine complexes of transition metals (Ru, Ir) that are photoactive in visible light but also organic photocatalysts. The radicals formed can thus be trapped by various radical acceptors. In addition, the bis-catecholato silicates can be employed in cross-coupling reactions with alkene halides and (hetero)aromatic halides under photoredox/nickel dual catalysis conditions for the formation of C(sp2) – C(sp3) bonds. The methodology can also be extended to C(sp3) – C (sp3) with some limitations. On the other hand, a study comparing the silicates and the "ate-complex" of boron for the formation of radicals by oxidation process is presented. Finally, promising works on the oxidation of silicates by copper complexes bearing non-innocent ligands have been initiated.
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Christophe Lévêque. Photooxidation of hypercoordinate silicate for the generation of carbon centered radicals : radical processes and dual catalysis. Catalysis. Université Pierre et Marie Curie - Paris VI, 2017. English. ⟨NNT : 2017PA066209⟩. ⟨tel-01754038⟩

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