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

ContributorsTortoreto, Cecilia
Defense date2014-03-21
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
  • Carbenes
  • Diazo compounds
  • Ruthenium
  • C-H insertion
  • Enol acetals ylides
  • Epoxides
Research groups
Citation (ISO format)
TORTORETO, Cecilia. Three atoms insertion and addition reactions of α-diazo-β-ketoesters catalyzed by CpRu-complexes. Doctoral Thesis, 2014. doi: 10.13097/archive-ouverte/unige:39204
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Creation07/07/2014 13:48:00
First validation07/07/2014 13:48:00
Update time14/03/2023 21:30:21
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