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Three atoms insertion and addition reactions of α-diazo-β-ketoesters catalyzed by CpRu-complexes

Defense Thèse de doctorat : Univ. Genève, 2014 - Sc. 4679 - 2014/03/21
Abstract The goal of this PhD was to explore the reactivity of acceptor/acceptor ruthenium metal carbenes toward several Lewis basic functional groups such as carbonyl-containing moieties and cyclic ethers. In fact, α-diazo-β-ketoesters and combinations of cationic [CpRu(CH3CN)3]+ complexes and diimine ligands selectively provided different classes of oxygen containing heterocycles in single step processes. In particular, a new reactivity was discovered in the presence of tetrahydrofuran moieties leading to original enol-acetal products through unexpected 1,3-C-H insertion reactions. Also, in a new development that uses epoxides as substrates, acceptor/acceptor ruthenium metal carbenes underwent three-atom insertions, rather than lead to the usual deoxygenation pathway. Original 1,4-dioxene motifs were obtained as single regio- and stereoisomers. A perfect syn stereochemistry was observed for the ring opening, which behaves as an SN1-like transformation otherwise.
Keywords CarbenesDiazo compoundsRutheniumC-H insertionEnol acetals ylidesEpoxides
URN: urn:nbn:ch:unige-392043
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Research group Groupe Lacour
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TORTORETO, Cecilia. Three atoms insertion and addition reactions of α-diazo-β-ketoesters catalyzed by CpRu-complexes. Université de Genève. Thèse, 2014. https://archive-ouverte.unige.ch/unige:39204

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Deposited on : 2014-08-06

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