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Sustainable functionalization of cyclic amides and imides with ruthenium catalysts : development, scope and mechanisms

Abstract : The sustainable synthesis of fine chemicals is an important topic in view to drive our society to a more environmentally respectful way of living. In this context, forming and breaking chemical bonds at will with high levels of selectivity is at the central core of chemical synthesis. Consequently, reducing the number of chemical steps towards the target molecules, avoiding the utilization of overstoichiometric amounts of hazardous reagents and diminishing chemical wastes are only some of the challenges to be addressed by a future green chemistry. In this PhD thesis, different strategies are developed to prepare highly-added value chemicals starting from very low-functionalized starting materials. Using ruthenium catalysts, which are more abundant and less expensive than other noble metals (i.e. Pd, Rh, Ir, etc.), it was found that cyclic amides and cyclic imides, which are important building blocks in biology and materials science, behave as excellent weak directing groups to functionalize traditionallybelieved inert aromatic C-H bonds. Particular focus was devoted to the formation of new C-O and C-C chemical bonds using readily availableand benchmark (air and moisture) stable carboxylic acids, alkenes and boronic acids, respectively, as coupling partners. These reactions led to excellent levels of selectivity (i.e. site, regio, stereo). Some derivatizations of the resulting compounds and the late-stage functionalization of a representative drug candidate were tackled to highlight the utility of these methodologies. In the course of these studies, an unexpected cleavage of phthalimides leading to secondary amides was identified in the presence of a ruthenium catalyst. Traditionally, phthalimides are cleaved in the presence of hydrazine to release primary amines, however, such unprecedented protodecarbonylation reaction fills the gap delivering secondary amides. The mechanisms associated to all these transformations were investigated experimentally to some extent with the aim to gain a better fundamental understanding.
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Yu-Chao Yuan. Sustainable functionalization of cyclic amides and imides with ruthenium catalysts : development, scope and mechanisms. Catalysis. Université Rennes 1, 2019. English. ⟨NNT : 2019REN1S059⟩. ⟨tel-02508308⟩

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