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<dc:title xml:lang="en">New strategies and catalysts for challenging olefin metathesis reactions</dc:title>
<dcterms:alternative xml:lang="fr">Nouvelles stratégies et catalyseurs pour des réactions de métathèse d'oléfines complexes</dcterms:alternative>
<dc:subject xml:lang="fr">Catalyse</dc:subject>
<dc:subject xml:lang="fr">Synthèse</dc:subject>
<dc:subject xml:lang="fr">Métathèse d'oléfines</dc:subject>
<dc:subject xml:lang="fr">Mécanisme</dc:subject>
<dc:subject xml:lang="fr">Chimie organométallique</dc:subject>
<dc:subject xml:lang="en">Catalysis</dc:subject>
<dc:subject xml:lang="en">Synthesis</dc:subject>
<dc:subject xml:lang="en">Olefin metathesis</dc:subject>
<dc:subject xml:lang="en">Mechanism</dc:subject>
<dc:subject xml:lang="en">Organometallic chemistry</dc:subject>
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<dcterms:abstract xml:lang="fr">La thèse présente la conception et le développement de nouvelles stratégies et catalyseurs pour des réactions de métathèse d'oléfines complexes.Le Chapitre Un décrit une métathèse croisée catalytique permettant d’accéder à des esters α,β-insaturés et fluorures d’acide trisubstitués Z et E. Un point clé est la conversion en une étape de l'acétate de lanostérol en acide 3-épi-anwuweizique (Z) et acide ganodérique Z (E).Le Chapitre Deux explore la synthèse d'alcènes Z-gem-Cl,CF3 par CM stéréosélective, alternative à la méthode stéréorétentive. Le rôle des alkylidènes Mo disubstitués est particulièrement notable. Le Chapitre Trois introduit une nouvelle classe de complexes cycliques à base de Mo, efficaces pour divers processus de métathèse, incluant la ROCM des cycloalcanes faiblement tendus, la CM d’oléfines trisubstituées et la première REMP contrôlée cinétiquement produisant des polymères cycliques riches en Z.</dcterms:abstract>
<dcterms:abstract xml:lang="en">The thesis presents the design and development of new strategies and catalysts for challenging olefin metathesis reactions.Chapter One introduces a catalytic cross-metathesis reactions that can access Z- and E-trisubstituted α,β-unsaturated esters and acid fluorides. A highlight of this method is the one-step conversion of lanosterol acetate to 3-epi-anwuweizic acid (Z) and ganoderic acid Z (E).Chapter Two focuses on the synthesis of Z-gem-Cl,CF3-substituted alkenes through stereoselective CM, an alternative to the previously established stereoretentive method. The investigations on the role of disubstituted Mo alkylidenes is noteworthy.Chapter Three introduces a new class of cyclic Mo-based complexes. They are uniquely effective in promoting various olefin metathesis processes. These include ring-opening/cross-metathesis of low-strain cycloalkenes, CM involving trisubstituted olefins, and the first kinetically controlled ring-expansion metathesis polymerization that affords Z-abundant cyclic polymers.</dcterms:abstract>
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